Heterocyclic alkoxyamines as regulators in controlled radical polymerization processes

ABSTRACT

The present invention is aimed at a process for controlled polymerization of ethylenically unsaturated monomers in the presence of heterocyclic sterically hindered alkoxyamine compounds. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator, as well as a process for polymerization are also subjects of the present invention. Still further subjects of the invention are novel amine precursors and a novel process for manufacturing 5-ring heterocyclic amines.

This is a divisional of application Ser. No. 09/417,538, filed on Oct.14, 1999, now U.S. Pat. No. 6,479,608.

The present invention relates to heterocyclic alkoxyamine compounds, apolymerizable composition comprising a) at least one ethylenicallyunsaturated monomer and b) a heterocyclic alkoxyamine compound. Furtheraspects of the present invention are a process for polymerizingethylenically unsaturated monomers, and the use of heterocyclicalkoxyamine compounds for controlled polymerization. The intermediateN-oxyl derivatives, a composition of the N-oxyl derivatives withethylenically unsaturated monomers and a free radical initiator, as wellas a process for polymerization are also subjects of the presentinvention. Further subjects of the invention are novel amine precursorsand a novel process for manufacturing 5-ring heterocyclic amines.

The compounds of the present invention provide polymeric resin productshaving low polydispersity. The polymerization process proceeds withenhanced monomer to polymer conversion efficiency. In particular, thisinvention relates to stable free radical-mediated polymerizationprocesses which provide homopolymers, random copolymers, blockcopolymers, multiblock copolymers, graft copolymers and the like, atenhanced rates of polymerization and enhanced monomer to polymerconversions.

Polymers or copolymers prepared by free radical polymerization processesinherently have broad molecular weight distributions or polydispersitieswhich are generally higher than about four. One reason for this is thatmost of the free radical initiators have half lives that are relativelylong, ranging from several minutes to many hours, and thus the polymericchains are not all initiated at the same time and the initiators providegrowing chains of various lengths at any time during the polymerizationprocess. Another reason is that the propagating chains in a free radicalprocess can react with each other in processes known as combination anddisproportionation, both of which are irreversibly chain-terminatingreaction processes. In doing so, chains of varying lengths areterminated at different times during the reaction process, resulting inresins consisting of polymeric chains which vary widely in length fromvery small to very large and which thus have broad polydispersities. Ifa free radical polymerization process is to be used for producing narrowmolecular weight distributions, then all polymer chains must beinitiated at about the same time and termination of the growingpolymer-chains by combination or disproportionation processes must beavoided.

Conventional radical polymerization reaction processes pose varioussignificant problems, such as difficulties in predicting or controllingthe molecular weight, the polydispersity and the modality of thepolymers produced. Furthermore, free radical polymerization processes inbulk of the prior art are difficult to control because thepolymerization reaction is strongly exothermic and an efficient heatremoval in the highly viscous polymer is mostly impossible. Theexothermic nature of the prior art free radical polymerization processesoften severely restricts the concentration of reactants or the reactorsize upon scale-up.

Due to the above mentioned uncontrollable polymerization reactions, gelformation in conventional free radical polymerization processes are alsopossible and cause broad molecular weight distributions and/ordifficulties during filtering, drying and manipulating the productresin.

U.S. Pat. No. 4,581,429 to Solomon et al., issued Apr. 8, 1986,discloses a free radical polymerization process which controls thegrowth of polymer chains to produce short chain or oligomerichomopolymers and copolymers, including block and graft copolymers. Theprocess employs an initiator having the formula (in part) R′R″N—O—X,where X is a free radical species capable of polymerizing unsaturatedmonomers. The reactions typically have low conversion rates.Specifically mentioned radical R′R″N—O• groups are derived from 1,1,3,3tetraethylisoindoline, 1,1,3,3 tetrapropylisoindoline, 2,2,6,6tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine ordi-t-butylamine. However, the suggested compounds do not fulfill allrequirements. Particularly the polymerization of acrylates does notproceed fast enough and/or the monomer to polymer conversion is not ashigh as desired.

WO 98/13392 describes open chain alkoxyamine compounds which have asymmetrical substitution pattern and are derived from NO gas or fromnitroso compounds.

EP-A-735 052 discloses a method for preparing thermoplastic polymers ofnarrow polydispersities by free radical-initated polymerization, whichcomprises adding a free radical initiator and a stable free radicalagent to the monomer compound.

WO 96/24620 describes a polymerization process in which very specificstable free radical agents are used, such as for example

WO 98/30601 discloses specific nitroxyls based on imidazolidinons.Nitroxylethers are generically mentioned but not specifically disclosed.

WO 98/44008 discloses specific nitroxyls based on morpholinones,piperazinones and piperazindiones. The nitroxylethers are alsogenerically mentioned but not specifically disclosed.

Despite the above mentioned attempts to improve the control of radicalpolymerization reactions there is still a need for new polymerizationregulators, which are highly reactive, and give an equally good orbetter control of the molecular weight of the polymer.

Surprisingly it has been found that particularly 5 and 6 memberedheterocyclic alkoxyamines or their nitroxyl precursors, which have ahigh sterical hindrance in α-position to the alkoxyamine group lead toregulators/initiators which allow polymerization very efficient and fastat higher temperatures, but also work at relatively low temperaturessuch as for example 100° C. The higher sterical hindrance may beintroduced by at least one higher alkyl substituent than methyl inα-position to the alkoxyamine group. In many cases even higher hindranceby two, three or four higher alkyl groups may be advantageous. Thehigher sterical hindrance may be also advantageous for 7 and 8 memberedheterocyclic alkoxyamines or their nitroxyl precursors.

One subject of the present invention is a polymerizable composition,comprising

a) at least one ethylenically unsaturated monomer or oligomer, and

b) a compound of formula (Ia) or (Ib)

wherein

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄ togetherwith the linking carbon atom form a C₃-C₁₂cycloalkyl radical;

with the proviso that if Q in formula (Ia) is a direct bond, —CH₂— orCO, at least one of R₁, R₂, R₃ or R₄ is different from methyl;

R₅, R₆ and R₇ independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl;

X represents a group having at least one carbon atom and is such thatthe free radical X• derived from X is capable of initiatingpolymerization of ethylenically unsaturated monomers;

Z₁ is O or NR₈;

R₈ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,C₁-C₁₈alkyl, C₃-CC₁₈alkenyl, C₃-C₁₈alkinyl which are substituted by oneor more OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkyl which isinterrupted by at least one O atom and/or NR₅ group, C₃-C₁₂cycloalkyl orC₆-C₁₀aryl, C₇-C₉phenylalkyl, C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl,—O—C₁-C₁₈alkyl or —COOC₁-C₁₈alkyl;

Q is a direct bond or a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ are independently hydrogen, phenyl or C₁-C₁₈alkyl;

with the proviso that the compounds (A) and (B) are excluded

Halogen is F, Cl, Br or I, preferably Cl or Br.

The alkyl radicals in the various substituents may be linear orbranched. Examples of alkyl containing 1 to 18 carbon atoms are methyl,ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl,2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as forexample propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl,3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl,n-2-octadecenyl oder n-4-octadecenyl. Preferred is alkenyl with 3 bis12, particularly preferred with 3 to 6 carbon atoms.

Alkinyl with 3 to 18 is a linear or branched radical as for examplepropinyl

2-butinyl, 3-butinyl, n-2-octinyl, oder n-2-octadecinyl. Preferred isalkinyl with 3 to 12, particularly preferred with 3 to 6 carbon atoms.

Examples for hydroxy substituted alkyl are hydroxy propyl, hydroxy butylor hydroxy hexyl.

Examples for halogen substituted alkyl are dichloropropyl,monobromobutyl or trichlorohexyl.

C₂-C₁₈alkyl interrupted by at least one O atom is for example—CH₂—CH₂—O—CH₂—CH₃, —CH₂—CH₂—O—CH₃— or—CH₂—CH₂—O—CH₂—CH₂—CH₂—O—CH₂—CH₃—. It is preferably derived frompolyethlene glycol. A general description is —((CH₂)_(a)—O)_(b)—H/CH₃,wherein a is a number from 1 to 6 and b is a number from 2 to 10.

C₂-C₁₈alkyl interrupted by at least one NR₅ group may be generallydescribed as —((CH₂)_(a)—NR₅)_(b)—H/CH₃, wherein a, b and R₅ are asdefined above.

C₃-C₁₂cycloalkyl is typically, cyclopropyl, cyclopentyl,methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl ortrimethylcyclohexyl.

C₆-C₁₀ aryl is for example phenyl or naphthyl, but also comprised areC₁-C₄alkyl substituted phenyl, C₁-C₄alkoxy substituted phenyl, hydroxy,halogen or nitro substituted phenyl. Examples for alkyl substitutedphenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene orisopropylbenzene. Halogen substituted phenyl is for exampledichlorobenzene or bromotoluene.

The C₁-C₄alkoxy substituents are methoxy, ethoxy, propoxy or butoxy andtheir corresponding isomers.

C₇-C₉phenylalkyl is benzyl, phenylethyl or phenylpropyl.

C₅-C₁₀heteroaryl is for example pyrrol, pyrazol, imidazol, 2,4,dimethylpyrrol, 1-methylpyrrol, thiophene, furane, furfural, indol,cumarone, oxazol, thiazol, isoxazol, isothiazol, triazol, pyridine,α-picoline, pyridazine, pyrazine or pyrimidine.

Preferred is a composition according, wherein in formula (Ia) and (Ib)R₁, R₂, R₃ and R₄ independently of each other are C₁-C₆alkyl, which isunsubstituted or substituted by OH, halogen or a group —O—C(O)—R₅,C₂-C₁₂alkyl which is interrupted by at least one O atom and/or NR₅group, C₅-C₆cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄together with the linking carbon atom form a C₅-C₆cycloalkyl radical.

More preferred is a composition, wherein in formula (Ia) and (Ib) R₁,R₂, R₃ and R₄ independently of each other are C₁-C₄alkyl, which isunsubstituted or substituted by OH, or a group —O—C(O)—R₅, or R₁ and R₂and/or R₃ and R₄ together with the linking carbon atom form aC₅-C₆cycloalkyl radical; and

R₅ is hydrogen or C₁-C₄alkyl.

Preferrably in formula (Ia) and (Ib) R₆ and R₇ independently arehydrogen, methyl or ethyl.

Preferably in formula (Ia) and (Ib) R₈ is hydrogen, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by OH; or C₇-C₉phenylalkyl.

More preferably in formula (Ia) and (Ib) R₈ is hydrogen, C₁-C₄alkyl,C₁-C₄alkyl which is substituted by OH; phenyl or benzyl.

Preferred is a composition, wherein in formula (Ia) and (Ib) R₉, R₁₀,R₁₁, R₁₂, R₁₃ and R₁₄ are independently hydrogen or C₁-C₄alkyl.

Preferred is a composition, wherein in formula (Ia) and (Ib) Q is adirect bond or a divalent radical CH₂, CH₂—CH₂, CH₂—CH₂—CH₂, C(O) orCH₂C(O), CH₂—CH—CH₃, CH₂—CH-phenyl, phenyl-CH—CH₂—CH-phenyl,phenyl-CH—CH₂—CH—CH₃, CH₂—CH(CH)₃—CH₂, C(CH₃)₂—CH-phenyl orC(CH₃)₂—CH₂—CH—CH₃.

Preferably in formula (Ia) and (Ib) X is selected from the groupconsisting of —CH(aryl)₂, —CH₂-aryl,

(C₅-C₆cycloalkyl)₂CCN, C₅-C₆cycloalkylidene-CCN, (C₁-C₁₂alkyl)₂CCN,—CH₂CH═CH₂, (C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₆-C₁₀)aryl,(C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₃₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₃₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₃₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₃₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-aryl,

—O—C(O)—C₁-C₁₂alkyl, —O—C(O)—(C₆-C₁₀)aryl,

(C₁-C₁₂)alkyl-CR₃₀—CN,

wherein

R₃₀ is hydrogen or C₁-C₁₂alkyl; and

the aryl groups are phenyl or naphthyl which are unsubstituted orsubstituted with C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy,C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COOC₁-C₁₂alkyl.

Aryl is preferably phenyl, which is unsubstituted or substituted asdescribed above.

More preferred is a composition, wherein in formula (Ia) and (Ib) X isselected from the group consisting of —CH₂-phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂ and O—C(O)-phenyl.

A preferred subgroup of compounds are those of formula (Ia) and (Ib),wherein R₁, R₂, R₃ and R₄ independently of each other are C₁-C₃alkyl,which is unsubstituted or substituted by OH, or a group —O—C(O)—R₅, orR₁ and R₂ and/or R₃ and R₄ together with the linking carbon atom form aC₅-C₆cycloalkyl radical;

R₅ is hydrogen or C₁-C₄alkyl.

R₆ and R₇ independently are hydrogen, methyl or ethyl;

Z₁ is O or NR₈;

Q is a direct bond or a divalent radical CH₂, CH₂CH₂, CH₂—CH₂—CH₂, C(O),CH₂C(O) or CH₂—CH—CH₃.

R₈ is hydrogen, C₁-C₄alkyl, C₁-C₄alkyl which is substituted by OH, orbenzyl; and

X is selected from the group consisting of CH₂-phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (CH₃)₂CCN, CH₂CH═CH₂, CH₃CH—CH═CH₂.

Another preferred composition is, wherein in formula (Ia) and (Ib) atleast two of R₁, R₂, R₃ and R₄ are ethyl, propyl or butyl and theremaining are methyl.

Another preferred subgroup is wherein at least three of R₁, R₂, R₃ andR₄ are ethyl, propyl or butyl.

The other substituents are as defined above including their preferences.

Particularly preferred is a composition, wherein the compound is offormula (Ic), (Id), (Ie), (If), (Ig) or (Ih)

wherein R₁ to R₁₂ and X have the meaning as defined above includingtheir preferences.

Within the above subgroup the compounds of formula (Id), (Ie), (Ig) or(Ih) are particularly preferred.

A further preferred subgroup within the compounds of formulae (Ic)-(Ih)are those, wherein

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₃alkyl, which isunsubstituted or substituted by OH, or a group —O—C(O)—R₅, or R₁ and R₂and/or R₃ and R₄ together with the linking carbon atom form aC₅-C₆cycloalkyl radical;

R₅ is hydrogen or C₁-C₄alkyl.

R₆ and R₇ independently are hydrogen, methyl or ethyl;

R₈ is hydrogen, C₁-C₄alkyl, C₁-C₄alkyl which is substituted by OH, orbenzyl;

R₉, R₁₀, R₁₁ and R₁₂ are independently hydrogen or C₁-C₄alkyl; and

X is selected from the group consisting of CH₂-phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (CH₃)₂CCN, CH₂CH═CH₂, CH₃CH—CH═CH₂.

More preferred are those, wherein the compound is of formula (Ie);

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₃alkyl, which isunsubstituted or substituted by OH, or a group —O—C(O)—R₅,

R₅ is hydrogen or C₁-C₄alkyl.

R₈ is hydrogen, C₁-C₄alkyl, C₁-C₄alkyl which is substituted by OH, orbenzyl;

R₉ and R₁₀ are hydrogen; and

X is selected from the group consisting of CH₂-phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (CH₃)₂CCN, CH₂CH═CH₂, CH₃CH—CH═CH₂.

Preferably the ethylenically unsaturated monomer or oligomer is selectedfrom the group consisting of ethylene, propylene, n-butylene,i-butylene, styrene, substituted styrene, conjugated dienes, acrolein,vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylicesters, (meth)acrylonitriles, (alkyl)acrylamides, vinyl halides orvinylidene halides.

Preferred ethylenically unsaturated monomers are ethylene, propylene,n-butylene, i-butylene, isoprene, 1,3-butadiene, α-C₅-C₁₈alkene,styrene, α-methyl styrene, p-methyl styrene or a compound of formulaCH₂═C(R_(a))—(C═Z)—R_(b), wherein R_(a) is hydrogen or C₁-C₄alkyl, R_(b)is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy, C₂-C₁₀₀alkoxyinterrupted by at least one N and/or O atom, or hydroxy-substitutedC₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino, di(C₁-C₁₈alkyl)amino,hydroxy-substituted C₁-C₁₈alkylamino or hydroxy-substituteddi(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂An⁻;

An⁻ is a anion of a monovalent organic or inorganic acid;

Me is a monovalent metal atom or the ammonium ion.

Z is oxygen or sulfur.

Examples of acids from which the anion An⁻ is derived areC₁-C₁₂carboxylic acids, organic sulfonic acids such as CF₃SO₃H orCH₃SO₃H, mineralic acids such as HCl, HBr or HI, oxo acids such as HClO₄or complex acids such as HPF₆ or HBF₄.

Examples for R_(a) as C₂-C₁₀₀alkoxy interrupted by at least one O atomare of formula

wherein R_(c) is C₁-C₂₅alkyl, phenyl or phenyl substituted byC₁-C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1 to 50.These monomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

wherein An⁻ and R_(a) have the meaning as defined above and R_(e) ismethyl or benzyl. An⁻ is preferably Cl⁻, Br⁻ or ⁻O₃S—CH₃.

Further acrylate monomers are

Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and

Z is oxygen.

Particularly preferred ethylenically unsaturated monomers are styrene,methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert.butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide ordimethylaminopropyl-methacrylamide.

It is also possible to enhance the rate of polymerization orcopolymerization of slowly polymerizing monomers such as for example ofthe class of methacrylates, in particular methylmethacrylate by theaddition of more readily polymerizable comonomers such as acrylates.Typical examples are the polymerization or copolymerization ofmethylmethacrylate in the presence of methylacrylate or butylacrylate.

Typical slowly polymerizing methacrylates are methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, methacrylamide ordimethylaminopropyl-methacrylamide. The polymerization of thesemethacrylates can be enhanced by the addition of the correspondingacrylates.

Also preferred is a composition, wherein the ethylenically unsaturatedmonomer is a mixture of a methacrylate and an acrylate.

The amounts of readily polymerizable comonomers range typically from 5parts to 95 and the slowly polymerizable monomers range from 95 to 5parts respectively.

The compound of formula (Ia) or (Ib) is preferably present in an amountof from 0.01 mol-% to 30 mol-%, more preferably in an amount of from0.05 mol-% to 20 mol-%, and most preferably in an amount of from 0.1mol-% to 10 mol-% based on the monomer or monomer mixture.

Another subject of the invention is a process for preparing an oligomer,a cooligomer, a polymer or a copolymer (block or random) by free radicalpolymerization of at least one ethylenically unsaturated monomer oroligomer, which comprises (co)polymerizing the monomer ormonomers/oligomers in the presence of an initiator compound of formula(Ia) or (Ib) as described above under reaction conditions capable ofeffecting scission of the O—X bond to form two free radicals, theradical •X being capable of initiating polymerization.

Preferably the scission of the O—X bond is effected by ultrasonictreatment, heating or exposure to electromagnetic radiation, rangingfrom γ to microwaves.

More preferably the scission of the O—X bond is effected by heating andtakes place at a temperature of between 50° C. and 160° C., morepreferably between 80° C. and 150° C.

After the polymerization step is completed the reaction mixture may becooled down to a temperature below 60° C., preferably to roomtemperature. The polymer may be stored at this temperature withoutfurther reactions occuring.

The process may be carried out in the presence of an organic solvent orin the presence of water or in mixtures of organic solvents and water.Additional cosolvents or surfactants, such as glycols or ammonium saltsof fatty acids, may be present. Other suitable cosolvents are describedhereinafter.

Preferred processes use as little solvents as possible. In the reactionmixture it is preferred to use more than 30% by weight of monomer andinitiator, particularly preferably more than 50% and most preferrablymore than 80%. In many cases it is possible to polymerize without anysolvent.

If organic solvents are used, suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),aromatic hydrocarbons (benzene, toluene, xylene), halogenatedhydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethyleneglycol, ethylene glycol monomethyl ether), esters (ethyl acetate,propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutylether, ethylene glycol dimethyl ether), or mixtures thereof.

The aqueous polymerization reactions can be supplemented with awater-miscible or hydrophilic cosolvent to help ensure that the reactionmixture remains a homogeneous single phase throughout the monomerconversion. Any water-soluble or water-miscible cosolvent may be used,as long as the aqueous solvent medium is effective in providing asolvent system which prevents precipitation or phase separation of thereactants or polymer products until after all polymerization reactionshave been completed. Exemplary cosolvents useful in the presentinvention may be selected from the group consisting of aliphaticalcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,polypropylene glycols, amides, carboxylic acids and salts thereof,esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,hydroxyether derivatives such as butyl carbitol or cellosolve, aminoalcohols, ketones, and the like, as well as derivatives thereof andmixtures thereof. Specific examples include methanol, ethanol, propanol,dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol,dipropylene glycol, tetrahydrofuran, and other water-soluble orwater-miscible materials, and mixtures thereof. When mixtures of waterand water-soluble or water-miscible organic liquids are selected as theaqueous reaction media, the water to cosolvent weight ratio is typicallyin the range of about 100:0 to about 10:90.

The process is particularly useful for the preparation of blockcopolymers.

Block copolymers are, for example, block copolymers of polystyrene andpolyacrylate (e.g., poly(styrene-co-acrylate) orpoly(styrene-co-acrylate-co-styrene). They are usefull as adhesives oras compatibilizers for polymer blends or as polymer toughening agents.Poly(methylmethacrylate-co-acrylate) diblock copolymers orpoly(methylacrylate-co-acrylate-co-methacrylate) triblock copolymers)are useful as dispersing agents for coating systeme, as coatingadditives (e.g. rheological agents, compatibilizers, reactive diluents)or as resin component in coatings(e.g. high solid paints) Blockcopolymers of styrene, (meth)acrylates and/or acrylonitrile are usefulfor plastics, elastomers and adhesives.

Furthermore, block copolymers of this invention, wherein the blocksalternate between polar monomers and non-polar monomers, are useful inmany applications as amphiphilic surfactants or dispersants forpreparing highly uniform polymer blends.

The (co)polymers of the present invention may have a number averagemolecular weight from 1 000 to 400 000 g/mol, preferably from 2 000 to250 000 g/mol and, more preferably, from 2 000 to 200 000 g/mol. Thenumber average molecular weight may be determined by size exclusionchromatography (SEC), matrix assisted laser desorption/ionization massspectrometry (MALDI-MS) or, if the initiator carries a group which canbe easily distinguished from the monomer(s), by NMR spectroscopy orother conventional methods.

The polymers or copolymers of the present invention have preferably apolydispersity of from 1.1 to 2, more preferably of from 1.2 to 1.8.

Thus, the present invention also encompasses in the synthesis novelblock, multi-block, star, gradient, random, hyperbranched and dendriticcopolymers, as well as graft copolymers.

The polymers prepared by the present invention are useful for followingapplications:

adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers,adhesion promoters, corrosion inhibitors, viscosity improvers,lubricants, rheology modifiers, thickeners, crosslinkers, papertreatment, water treatment, electronic materials, paints, coatings,photography, ink materials, imaging materials, superabsorbants,cosmetics, hair products, preservatives, biocide materials or modifiersfor asphalt, leather, textiles, ceramics and wood.

Because the present polymerizaton is a “living” polymerization, it canbe started and stopped practically at will. Furthermore, the polymerproduct retains the functional alkoxyamine group allowing a continuationof the polymerization in a living matter. Thus, in one embodiment ofthis invention, once the first monomer is consumed in the initialpolymerizing step a second monomer can then be added to form a secondblock on the growing polymer chain in a second polymerization step.Therefore it is possible to carry out additional polymerizations withthe same or different monomer(s) to prepare multi-block copolymers.Furthermore, since this is a radical polymerization, blocks can beprepared in essentially any order. One is not necessarily restricted topreparing block copolymers where the sequential polymerizing steps mustflow from the least stabilized polymer intermediate to the moststabilized polymer intermediate, such as is the case in ionicpolymerization. Thus it is possible to prepare a multi-block copolymerin which a polyacrylonitrile or a poly(meth)acrylate block is preparedfirst, then a styrene or butadiene block is attached thereto, and so on.

Furthermore, there is no linking group required for joining thedifferent blocks of the present block copolymer. One can simply addsuccessive monomers to form successive blocks.

A plurality of specifically designed polymers and copolymers areaccessible by the present invention, such as star and graft (co)polymersas described, inter alia, by C. J. Hawker in Angew. Chemie, 1995, 107,pages 1623-1627, dendrimers as described by K. Matyaszewski et al. inMacromolecules 1996, Vol 29, No. 12, pages 4167-4171, graft (co)polymersas described by C. J. Hawker et al. in Macromol. Chem. Phys. 198,155-166(1997), random copolymers as described by C. J. Hawker inMacromolecules 1996, 29, 2686-2688, or diblock and triblock copolymersas described by N. A. Listigovers in Macromolecules 1996, 29, 8992-8993.

Another subject of the present invention is a polymer or oligomer havingattached at least one initiator group —X and at least one oxyamine groupof formula (Xa) or (Xb)

wherein R₁ to R₇, Q and Z₁ are as defined above including theirpreferences.

The majority of compounds of formula (Ia) and (Ib) is novel and they areconsequently also subject of the present invention.

The new compounds are of formula (IIa) or (IIb)

wherein

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄ togetherwith the linking carbon atom form a C₃-C₁₂cycloalkyl radical;

with the proviso that if Q in formula (Ia) is a direct bond, —CH₂— orCO, at least one of R₁, R₂, R₃ or R₄ is different from methyl;

R₅, R₆ and R₇ independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl;

X is selected from the group consisting of —CH(aryl)₂, —CH₂-aryl,

 —CH₂—CH₂-aryl,

 (C₅-C₆cycloalkyl)₂CCN, C₅-C₆cycloalkylidene-CCN, (C₁-C₁₂alkyl)₂CCN,—CH₂CH═CH₂, (C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₆-C₁₀)aryl,(C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₁-C₁₂)alkoxy, (C₁-C₁₂)alkyl-CR₃₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₃₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₃₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₃₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

 —O—C(O)—C₁-C₁₂alkyl, —O—C(O)—(C₆-C₁₀)aryl, (C₁-C₁₂)alkyl-CR₃₀—CN,

wherein

R₃₀ is hydrogen or C₁-C₁₂alkyl;

Z₁ is O or NR₈;

R₈ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl which are substituted by oneor more OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkyl which isinterrupted by at least one O atom and/or NR₅ group, C₃-C₁₂cycloalkyl orC₆-C₁₀aryl, C₇-C₉phenylalkyl, C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl,—O—C₁-C₁₈alkyl or COOC₁-C₁₈alkyl;

Q is a direct bond or a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ are independently hydrogen, phenyl or C₁-C₁₈alkyl; and

the aryl groups are phenyl or naphthyl which are unsubstituted orsubstituted with C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy,C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COOC₁-C₁₂alkyl;

with the proviso that the compounds (A) and (B) are excluded

In particular the compounds are of formula (IIc), (IId), (IIe), (IIf),(IIg) or (IIh)

wherein R₁ to R₁₂ have the meaning as defined above and

X is selected from the group consisting of —CH₂-phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂ and O—C(O)-phenyl.

Examples of the different substituents including their preferences havealready been given with regard to the composition and apply also for thecompounds of formula (IIa) and (IIb).

The compounds of formula (Ia), (Ib), (IIa) or (IIb) in general may beprepared according to standard methods, starting from the correspondingN—H compound, from which the corresponding N—O• compounds are prepared,and which are further reacted to the corresponding N—O—X compounds. Adetailed description is outlined below.

Summary of suitable methods for the preparation of the amine (N—H)precursors.

1. Subgroup

The compounds of formula

are for example accessible by reacting an amino alcohol with a ketoneand for example chloroform under basic conditions. The resultinghydroxycarboxylate is subsequently reacted to the cyclic lactone

The reaction is described for 6 membered rings by J. T. Lai.: Synthesis,122 (1984). The meaning of Q is in this case CR₉R₁₀.

2. Subgroup.

The compounds of formula

are for example accessible by a ring forming reaction with a diol

The reaction is described for morpholines by J. T. Lai.: Synthesis, 122(1984). Q has the meaning CR₉R₁₀.

3. Subgroup.

The piperazinones of formula

are prepared by reacting a diamine with chloroform and a ketone in thepresence of NaOH (J. T. Lai.: Synthesis, 40 (1981). Q is CR₉R₁₀.

The analogue reaction may be used for the preparation of 7 memberedrings (Pyong-nae Son et al.: J. Org. Chem. 46, 323 (1981). Q isCH₂—CR₉R₁₀.

4. Subgroup.

6-membered rings (piperazindione) of formula

may for example prepared from aminodinitriles according to E. F. J.Duynstee et al.: Recueil 87, 945 (1968).

5. Subgroup.

The lactames of formula

may be prepared by Beckmann rearrangement of the corresponding oximes.Another possibility is the Schmidt-Reaction as described by S. C.Dickermann et. al.: J. Org. Chem. 14, 530, (1949)):

6. Subgroup.

The preparation of compounds of formula

is for example described by T. Toda et. al.: Bull. Chem. Soc. Japan, 44,3445 (1971) or by Te-Chen Tsao et al.: Biotechnol. Prog. 7, 60 (1991).

However the known methods lead only to compounds wherein only two of R₁,R₂, R₃ or R₄ are higher alkyl than methyl.

A further subject of the present invention is therefore a process forthe preparation of a compound of formula (Vc)

wherein R₁, R₂, R₃ and R₄ are independently C₁-C₁₈alkyl, with theproviso that at least 3 are other than methyl and R₈ is as definedabove; by reacting a 1,1-dialkylglycinamide of formula (XXI)

with a ketone of formula XXII

under acid catalysis in an inert solvent to a compound of formula (Vc)

The reaction is typically carried out in excess of the correspondingketone or an inert solvent. Suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),aromatic hydrocarbons (benzene, toluene, xylene), halogenatedhydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethyleneglycol, ethylene glycol monomethyl ether), esters (ethyl acetate,propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutylether, ethylene glycol dimethyl ether), or mixtures thereof.

Typical acid catalysts are mineral acids like HCl, H₂SO₄, BF₃, acidicion-exchanger resins, acidic clays and montmorrilonites or strongorganic acids like oxalic acid.

The reaction is carried out under normal pressure at a temperatureranging from room temperature to the boiling temperature of the reactionmixture.

Typically the reaction time is 1 to 100 h, preferably 1 to 20 hours.

The N—H precursors of the corresponding N—O—X compounds of formula (Ia)and (Ib) are partly new.

The new compounds are therefore also subject of the present invention.Subject of the invention is a compound of formula (IVa) or (IVb)

wherein

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl;

R₅, R₆ and R₇ independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl;

Z₁ is O or NR₈;

R₈ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl which are substituted by oneor more OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkyl which isinterrupted by at least one O atom and/or NR₅ group, C₃-C₁₂cycloalkyl orC₆-C₁₀aryl, C₇-C₉phenylalkyl, C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl,—O—C₁-C₁₈alkyl or —COOC₁-C₁₈alkyl;

Q is a direct bond or a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ are independently hydrogen, phenyl or C₁-C₁₈alkyl;

with the proviso that if the compounds of formula (IVa) or (IVb)represent a 5, 6 or 7 membered ring at least two of R₁, R₂, R₃ and R₄are different from methyl and the substitution patterns R₁, R₂, R₃, R₄being methyl, methyl, butyl, butyl or methyl, ethyl, methyl, ethyl areexcluded.

Preferred is a compound, wherein R₁, R₂, R₃ and R₄ independently of eachother are C₁-C₄alkyl, which is unsubstituted or substituted by OH, or agroup —O—C(O)—R₅, with the proviso that if the compounds of formula(IVa) or (IVb) represent a 5, 6 or 7 membered ring at least two of R₁,R₂, R₃ and R₄ are different from methyl and the substitution patternsmethyl methyl, butyl, butyl or methyl, ethyl, methyl, ethyl areexcluded;

R₅ is hydrogen or C₁-C₄alkyl.

R₆ and R₇ independently are hydrogen, methyl or ethyl;

Z₁ is O or NR₈;

Q is a direct bond or a divalent radical CH₂, CH₂CH₂, CH₂—CH₂—CH₂, C(O),CH₂C(O) or CH₂—CH—CH₃;

R₈ is hydrogen, C₁-C₄alkyl or C₁-C₄alkyl which is substituted by OH, orbenzyl.

More preferred is a compound wherein at least three of R₁, R₂, R₃ and R₄are different from methyl.

Examples of the different substituents including their preferences havealready been given and apply also for the compounds of formula (IVa) and(IVb).

As already mentioned the compounds of formula (IVa) and (IVb) areprecursors which are oxidized to the corresponding N—O• compounds.

The oxidation of amines to the corresponding nitroxides is well knownand a review is given for example by L. B. Volodarsky, V. A. Reznikov,V. I. Ovcharenko.: Synthetic Chemistry of Stable Nitroxides, CRC Press,Boca Raton 1994.

The N—O• precursors of the corresponding N—O—X compounds of formula (Ia)and (Ib) are also partly new.

These new compounds are therefore also subject of the present invention.

A further subject of the invention is a compound of formula (IIIa) or(IIIb)

wherein

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄ togetherwith the linking carbon atom form a C₃-C₁₂cycloalkyl radical;

R₅, R₆ and R₇ independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl;

Z₁ is O or NR₈;

R₈ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl which are substituted by OH,halogen or a group —O—C(O)—R₅, C₂-C₁₈alkyl which is interrupted by atleast one O atom and/or NR₅ group, C₃-C₁₂cycloalkyl or C₆-C₁₀aryl,C₇-C₉phenylalkyl, C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl, —O—C₁-C₁₈alkyl or—COOC₁-C₁₈alkyl;

Q is a direct bond or a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ are independently hydrogen, phenyl or C₁-C₁₈alkyl;

with the proviso that in formula (IIIa)

if Q is a direct bond and Z₁ is NR₈, at least three of R₁, R₂, R₃ or R₄are higher alkyl than methyl;

or if Q is CH₂ and Z₁ is O, at least one of R₁, R₂, R₃ or R₄ is higheralkyl than methyl;

or if Q is CH₂ or C(O) and Z₁ is NR₈ at least two of R₁, R₂, R₃ or R₄are higher alkyl than methyl or one is higher alkyl than methyl and R₁and R₂ or R₃ and R₄ form a C₃-C₁₂cycloalkyl radical together with thelinking carbon atom.

Preferred is a compound, wherein R₁, R₂, R₃ and R₄ independently of eachother are C₁-C₄alkyl, which is unsubstituted or substituted by OH or agroup —O—C(O)—R₅;

R₅ is hydrogen or C₁-C₄alkyl.

R₆ and R₇ independently are hydrogen, methyl or ethyl;

Z₁ is O or NR₈;

Q is a direct bond or a divalent radical CH₂, CH₂CH₂, CH₂—CH₂—CH₂, C(O),CH₂C(O) or CH₂—CH—CH₃;

R₈ is hydrogen, C₁-C₄alkyl or C₁-C₄alkyl which is substituted by OH, orbenzyl; with the proviso that in formula (IIIa)

if Q is a direct bond and Z₁ is NR₈, at least three of R₁, R₂, R₃ or R₄are higher alkyl than methyl;

or if Q is CH₂ and Z₁ is O, at least one of R₁, R₂, R₃ or R₄ is higheralkyl than methyl;

or if Q is CH₂ or C(O) and Z₁ is NR₈ at least two of R₁, R₂, R₃ or R₄are higher alkyl than methyl or one is higher alkyl than methyl and R₁and R₂ or R₃ and R₄ form a C₃-C₁₂cycloalkyl radical together with thelinking carbon atom.

Examples of the different substituents including their preferences havealready been given and apply also for the compounds of formula (IIIa)and (IIIb).

These compounds are intermediates of the title compounds and may also beused together with a radical source to effect polymerization ofethylenically unsaturated monomers or oligomers.

Consequently a further subject of the invention is a polymerizablecomposition, comprising

a) at least one ethylenically unsaturated monomer or oligomer, and

b) a compound of formula (IIIa) or (IIIb)

wherein

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄ togetherwith the linking carbon atom form a C₃-C₁₂cycloalkyl radical;

R₅, R₆ and R₇ independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl;

Z₁ is O or NR₈;

R₈ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,C₁-C₁₈alkyl, C₃-C₁₈alkinyl, C₃-C₁₈alkinyl which are substituted by OH,halogen or a group —O—C(O)—R₅, C₂-C₁₈alkyl which is interrupted by atleast one O atom and/or NR₅ group, C₃-C₁₂cycloalkyl or C₆-C₁₀aryl,C₇-C₉phenylalkyl, C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl, —O—C₁-C₁₈alkyl or—COOC₁-C₁₈alkyl;

Q is a direct bond or a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ are independently hydrogen, phenyl or C₁-C₁₈alkyl;

with the proviso that in formula (IIIa)

if Q is a direct bond and Z₁ is NR₈, at least three of R₁, R₂, R₃ or R₄are higher alkyl than methyl;

or if Q is CH₂ and Z₁ is O, at least one of R₁, R₂, R₃ or R₄ is higheralkyl than methyl;

or if Q is CH₂ or C(O) and Z₁ is NR₈ at least two of R₁, R₂, R₃ or R₄are higher alkyl than methyl or one is higher alkyl than methyl and R₁and R₂ or R₃ and R₄ together with the linking carbon atom form aC₃-C₁₂cycloalkyl radical;

c) a free radical source capable of initiating polymerization ofethylenically unsaturated monomers.

Preferred is a composition, wherein the compound is of formula (IIIc),(IIId), (IIIe), (IIIf), (IIIg) or (IIIh)

wherein R₁ to R₁₂ have the meaning as defined defined above.

Examples for the different substituents including their preferences havealready been given. They apply also for the compounds in the abovecomposition.

The production of C-centered radicals is described, inter alia, inHouben Weyl, Methoden der Organischen Chemie, Vol. E 19a, pages 60-147.These methods can be applied in general analogy.

The source of radicals may be a bis-azo compound, a peroxide or ahydroperoxide.

Preferably, the source of radicals is 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride,2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide.

Preferred peroxides and hydroperoxides are acetyl cyclohexane sulphonylperoxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate,t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate,bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoylperoxide, dioctanoyl peroxide, dilauroyl peroxide, bis (2-methylbenzoyl)peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoylperoxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide,t-butyl perisobutyrate, t-butyl permaleinate,1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate,t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butylperacetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis(t-butylperoxy) butane, 2,2 bis (t-butylperoxy) propane, dicumylperoxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy3-phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxy isopropyl)benzene, 3,5-bis (t-butylperoxy)3,5-dimethyl 1,2-dioxolane, di-t-butylperoxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthanehydroperoxide, pinane hydroperoxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

These compounds are commercially available.

If more than one radical source is used, a mixture of substitutionpatterns is obtainable.

The molar ratio of the radical source to the compound of formulae IIIaor IIIb may be from 1:10 to 10:1, preferably from 1:5 to 5:1 and morepreferably from 1:2 to 2:1.

The NOX compounds are prepared for example by reacting the Nitroxideswith free radicals. The radicals may be generated by scission of peroxy-or azo compounds as for example described by T. J. Connolly, M. V.Baldovi, N. Mohtat, J. C. Scaiano.: Tet. Lett. 37, 4919 (1996) or by I.Li, B. A. Howell et al.: Polym. Prepr. 36, 469 (1996). Suitable examplesare given above.

Another possibility is a halogen atom transfer from a alkylhalogenide inthe presence of Cu(I) as described by K. Matyjaszewski.: Macromol. Symp.111, 47-61 (1996).) or a one electron oxidation as described by P.Stipa, L. Greci, P. Carloni, E. Damiani.: Polym. Deg. Stab. 55, 323(1997))

Further possibilities are the O-alkylation of the correspondinghydroxylamine, as for example described by Said Oulad Hammouch, J. M.Catala.: Macromol. Rapid Commun. 17, 149-154 (1996), Meisenheinmerrearrangement of the corresponding N-Allyl-N-oxids as described by B.Walchuk et al.: Polymer Preprints 39, 296 (1998) or the reaction of aoxoammonium salt with a carbonyl compound, as described by Tan Ren,You-Cheng Liu, Qing-Xiang Guo.: Bull. Chem. Soc. Jpn. 69, 2935 (1996).

Still further subjects of the invention are the use of a compound offormula (Ia) or (Ib) and the use of a compound of formula (IIIa) or(IIIb) together with a free radical source as defined above for thepolymerization of ethylenically unsaturated monomers or oligomers.

The following examples illustrate the invention.

EXAMPLES

5-Ring Compounds

Example A11-(1-cyanocyclohexyloxy)-2,5-dicyclohexylidene-imidazolidin-4-one (101)

1.2 g (0.005 mol) of 2,5-dicyclohexylidene-imidazolidin-4-on-1-oxyl(prepared in accordance with T. Toda et al.: Bull. Chem. Soc. Japan 44,3445 (1971)) and 1.25 g (0.005 mol) of1,1′-azobis(cyclohexanecarbonitrile) are refluxed for 16 hours undernitrogen in 20 ml of benzene. The benzene is then removed bydistillation in a rotary evaporator and the residue is chromatographedover silica gel with dichloromethane/ethyl acetate (19:1). The purefractions are concentrated to dryness by evaporation, made into a slurrywith hexane, filtered and and then dried.

This gives 0.5 g (29%) of compound (101), m.p. 240-242° C.(degradation).

Analysis calculated for C₂₀H₃₁N₃O₂: C 69.53%, H 9.04%, N 12.16%; found C69.32%, H 9.11%, N 12.19%.

Example A21-(dimethylcyanomethyloxy)-2,5-diethyl-2,5-dimethylimidazolidin-4-one(102)

3.1 g (0.0167 mol) of 2,5-diethyl-2,5-dimethylimidazolidin-4-on-1-oxyl(prepared in accordance with T. Toda et al.: Bull. Chem. Soc. Japan 44,3445 (1971)) and 4.1 g (0.0167 mol) of azobisisobutyronitrile arestirred for 17 hours at 75° C. under nitrogen in 20 ml of benzene. Thebenzene is then removed by distillation in a rotary evaporator and theresidue is chromatographed over silica gel with hexane/ethyl acetate(1:1). The pure fractions are concentrated to dryness by evaporation,made into a slurry with hexane, filtered and then dried.

This gives 2.9 g (68.5%) of compound (102), m.p. 118-121° C.(degradation).

Analysis calculated for C₁₃H₂₃N₃O₂: C 61.63%, H 9.15%, N 16.59%; found C61.62%, H 9.15%, N 16.61%.

Example A3 2,2,5,5-tetraethylimidazolidin-4-one (103)

26.5 g (0.2 mol) of 1,1-diethylglycinamide (prepared in accordance withSafir et. al.: J. Amer. Chem. Soc., 77, 4840 (1955)), 70 ml ofdiethylketone, 1.95 g (0.01 mol) of p-to-luenesulfonic acid and 0.5 mlof n-octylmercaptane are refluxed for 72 hours in a water separator.After cooling, the reaction mixture is washed with water, dried overMgSO₄, concentrated by evaporation in a rotary evaporator andrecrystallised from hexane.

This gives 30.65 g (77%) of compound (103), m.p. 68-70° C.

Analysis calculated for C₁₁H₂₂N₂O: C 66.62%, H 11.18%, N 14.13%; found C66.41%, H 11.07%, N 14.10%.

Example A4 2,2,5,5-tetraethylimidazolidin-4-on-1-oxyl (104)

A solution of 25.9 g (0.105 mol) of m-chloroperbenzoic acid (70%) in 50ml of ethyl acetate is added dropwise, with stirring, at 10° C. to asolution of 13.9 g (0.070 mol) of 2,2,5,5-tetraethylimidazolidin-4-onein 75 ml of ethyl acetate. This mixture is stirred for 24 hours at roomtemperature and is then charged with another 5 g of m-chloroperbenzoicacid (70%) and stirred for 20 hours. Subsequently, it is washed with3×100 ml of 1M NaHCO₃, dried over MgSO₄ and concentrated by evaporationin a rotary evaporator. The residue is chromatographed over silica gelwith hexane/ethyl acetate (2:1). The pure fractions are concentrated todryness by evaporation and recrystallised from hexane.

This gives 8.65 g (58%) of compound (104), m.p. 110-112° C.

Analysis calculated for C₁₁H₂₁N₂O₂: C 61.94%, H 9.92%, N 13.13%; found C61.84%, H 10.08%, N 13.04%.

Example A51-(dimethylcyanomethyloxy)-2,2,5,5-tetraethylimidazolidin-4-one (105)

4.3 g (0.022 mol) of 2,2,5,5-tetraethylimidazolidin-4-on-1-oxyl and 3.0g (0.018 mol) of azobisisobutyronitrile are refluxed for 8 hours undernitrogen in 15 ml of benzene. The benzene is then removed by evaporationin a rotary evaporator and the residue is chromatographed over silicagel with hexane/ethyl acetate (3:1). The pure fractions are concentratedto dryness by evaporation and recrystallised fromhexane/dichloromethane. This gives 3.95 g (65%) of compound (105), m.p.125-130° C. (degradation). Analysis calculated for C₁₅H₂₇N₃O₂: C 64.03%,H 9.67%, N 14.93%; found C 64.00%, H 9.86%, N 14.94%.

Example A6 1-(α-methylbenzyloxy)-2,2,5,5-tetraethylimidazolidin-4-one(106)

4.14 g (0.019 mol) of 2,2,5,5-tetraethylimidazolidin-4-on-1-oxyl aredissolved in 250 ml of ethylbenzene and charged with 14.3 ml (0.078 mol)of di-tert-butylperoxide. This solution is then irradiated untilcolourless in a Pyrex photoreactor under nitrogen at room temperatureusing a mercury lamp. The ethylbenzene is then removed by distillationin a rotary evaporator and the residue is recrystallised from pentane.

This gives 4.96 g (80%) of compound (106), m.p. 153-157° C.(degradation).

Analysis calculated for C₁₉H₃₀N₂O₂: C 71.66%, H 9.49%, N 8.80%; found C71.54%, H 9.58%, N 8.87%.

6-Ring Compounds

Example B1 3-ethyl-3,3,5-trimethylmorpholin-2-on-4-oxyl (204)

A solution of 42.5 g (0.172 mol) of m-chloroperbenzoic acid (70%) in 70ml of ethyl acetate is added dropwise, with stirring, to a solution of19.7 g (0.115 mol) of 3-ethyl-3,5,5-trimethylmorpholin-2-one (preparedin accordance with J. T. Lai.: Synthesis 122 (1984)) in 80 ml of ethylacetate at 10° C. The reaction mixture is stirred for another 12 hoursat room temperature and is then washed with 3×120 ml of 1 M NaHCO₃ andwith water, dried over MgSO₄ and concentrated by evaporation in a rotaryevaporator. The residue is chromatographed over silica gel with ethylacetate/hexane (1:2). The pure fractions are concentrated to dryness byevaporation and are recrystallised from hexane.

This gives 19 g (89%) of compound (204), m.p. 48-50° C.

Analysis calculated for C₉H₁₆NO₃: C 58.05%, H 8.66%, N 7.52%; found C58.10%, H 8.70%, N 7.42%.

Example B24-(dimethylcyanomethyloxy)-3-ethyl-3,5,5-trimethylmorpholin-2-one (205)

4.1 g (0.022 mol) of 3-ethyl-3,3,5-trimethylmorpholin-2-on-4-oxyl and2.7 g (0.017 mol) of azobisisobutyronitrile are refluxed under nitrogenin 8 ml of benzene for 2.5 hours. The benzene is then removed bydistillation in a rotary evaporator and the residue is chromatographedover silica gel with hexane/ethyl acetate (4:1). The pure fractions areconcentrated to dryness by evaporation and are recrystallised fromhexane/ethyl acetate.

This gives 5.3 g (96%) of compound (205), m.p. ˜71° C.

¹H-NMR (CDCl₃), d(ppm): 4.17 d (1H), 3.90 d (1H), 1.95 m (CH₂), 1.67 s2×(CH₃), 1.60 s (CH₃), 1.21 s (CH₃), 1.20 s (CH₃), 1.02 t (CH₃),

Example B3 4-(α-methylbenzyloxy)-3-ethyl-3,5,5-trimethylmorpholin-2-one(206)

A photoreactor is charged with 210 ml of ethylbenzene, 4.81 g (0.026mol) of 3-ethyl-3,5,5-trimethyl-morpholin-2-on-4-oxyl and 15.3 g (0.105mol) of t-butylperoxide. The red solution is rinsed with nitrogen and isthen irradiated under nitrogen at 20-25° C. using a mercury dipping lamp(Pyrex coat). After about 8 hours, the solution has lost its colour. Thereaction mixture is concentrated by evaporation in a rotary evaporator,resulting in 6.0 g (80%) of the desired compound in the form of aslightly yellow oil.

Elemental analysis calculated for C₁₇H₂₅NO₃: C 70.07%; H 8.65%; N 4.81%.Found: C 70.67%; H 8.46%; N 4.53%.

Example B4 3,3-diethyl-5,5-dimethylmorpholin-2-one (207)

120 g (3 mol) of finely ground sodium hydroxide are added, withstirring, to a solution of 53.5 g (0.6 mol) of 2-amino-2-methylpropanoland 73 ml (0.9 mol) of chloroform in 635 ml (6 mol) of diethylketone at5-10° C. The reaction mixture is stirred at room temperature for 16hours and is then filtered. The solid is made into a slurry with 2×350ml of methanol and filtered. The filtrates are concentrated to drynessby evaporation in a rotary evaporator and the residue is charged with200 ml of 32% hydrochloric acid and 100 ml of water and refluxed for 6hours. Subsequently, 600 ml of toluene are added and the water iscompletely removed by distillation in a water separator. 91 ml (0.66mol) of triethylamine are then added dropwise to the toluene solutionand the mixture is refluxed for another 6 hours. The precipitatedtriethylamine hydrochloride is removed by filtration and the filtrate issubjected to distillation at 123-127° C./20 mbar, giving compound (207)in the form of a colourless liquid, yield 63.7 g (57%).

¹H-NMR (CDCl₃), d(ppm): 4.11 s (CH₂), 1.90-1.60 m 2×(CH₂), 1.20 s2×(CH₃), 0.96 t 2×(CH₃).

Example B5 3,3-diethyl-5,5-dimethylmorpholin-2-on-4-oxyl (208)

32.2 g (0.165 mol) of peracetic acid (39% in acetic acid) are addeddropwise to a solution of 20.4 g (0.110 mol) of3,3-diethyl-5,5-dimethylmorpholin-2-one in 120 ml of ethyl acetate at 5°C. The reaction mixture is stirred for 6 hours at room temperature andis then washed with 120 ml of 1 M NaHCO₃ and with water, dried overMgSO₄ and concentrated by evaporation in a rotary evaporator. Theresidue is recrystallised from hexane.

This gives 20.4 g (92%) of compound (208), m.p. ˜63° C.

Analysis calculated for C₁₀H₁₈NO₃: C 59.98%, H 9.06%, N 6.99%; found C59.81%, H 9.07%, N 6.97%.

Example B64-(dimethylcyanomethyloxy)-3,3-diethyl-5,5-dimethylmorpholin-2-one (209)

5.0 g (0.025 mol) of 3,3-diethyl-5,5-dimethylmorpholin-2-on-4-oxyl and3.0 g (0.019 mol) of azobisisobutyronitrile are refluxed for 6.5 hoursunder nitrogen in 8 ml of benzene. The benzene is then removed bydistillation in a rotary evaporator and the residue is recrystallisedfrom hexane/benzene.

This gives 6.15 g (91%) of compound (209), m.p. ˜83° C.

¹H-NMR (CDCl₃), d(ppm): 4.08 d (1H), 3.99 d (1H), 2.2-1.8 m 2×(CH₂),1.67 s 2×(CH₃), 1.22 s (CH₃), 1.20 s (CH₃), 1.02 t 2×(CH₃).

Example B7 4-(α-methylbenzyloxy)-3,3-diethyl-5,5-dimethylmorpholin-2-one(210)

In analogy to Example B3, compound (206), 4.75 g (0.026 mol) of3,3-diethyl-5,5-dimethylmorpholin-2-on-4-oxyl are reacted witht-butylperoxide and ethylbenzene as solvent, resulting in 4.1 g (52%) ofcompound (210) in the form of a colourless oil.

Elemental analysis calculated for C₁₈H₂₇NO₃: C 70.79%; H 8.91%; N 4.59%.Found: C 71.67%; H 8.74%; N 4.46%.

Example B8 3,3,5,5-tetraethylmorpholin-2-one (211)

In analogy to Example B4 (compound 207), 4.35 g (23%) of compound (211)are obtained in the form of a colourless oil from 10.2 g (0.087 mol) of2-amino-2,2-diethylethanol (prepared in accordance with L. Villa et al.:II Farmaco 23, 441 (1968)), 11 ml (0.13 mol) of chloroform, 92 ml (0.87mol) of diethylketone and 17.4 g (0.43 mol) of sodium hydroxide.

Analysis calculated for C₁₂H₂₃NO₂: C 67.57%, H 10.87%, N 6.57%; found C67.46%, H 10.91%, N 6.49%.

Example B9 3,3,5,5-tetraethylmorpholin-2-on-4-oxyl (212)

0.05 g of sodium tungstate are added to a solution of 4.2 g (0.02 mol)of 3,3,5,5-tetraethylmorpholin-2-one in 25 ml of ethyl acetate and then5.85 g (0.03 mol) of peracetic acid (39% in acetic acid) are addeddropwise at 5° C. The reaction mixture is stirred for 24 hours at roomtemperature and is then washed with 1 M NaHCO₃ and water, dried overMgSO₄ and concentrated by evaporation in a rotary evaporator.

This gives 4.5 g (98%) of compound (212) in the form of a red oil.

Analysis calculated for C₁₂H₂₂NO₃: C 63.13%, H 9.71%, N 6.13%; found C63.13%, H 9.69%, N 6.26%.

Example B10 4-(α-methylbenzyloxy)-3,3,5,5-tetraethylmorpholin-2-one(213)

1.03 g (0.0045 mol) of 3,3,5,5-tetraethylmorpholin-2-on-4-oxyl aredissolved in 200 ml of ethylbenzene and charged with 3.3 ml (0.018 mol)of di-tert-butylperoxide. The solution is irradiated until colourless ina Pyrex photoreactor under nitrogen at room temperature using a mercurylamp. The ethylbenzene is removed by distillation in a rotary evaporatorand the residue is chromatographed over silica gel with hexane/ethylacetate 14:1). The pure fractions are concentrated by evaporation,giving 1.0 g (67%) of compound (213) in the form of a colourless oil.

Analysis calculated for C₂₀H₃₁NO₃: C 72.04%, H 9.37%, N 4.20%; found C71.76%, H 9.35%, N 3.93%.

Example B11 3,3,5-trimethyl-5-pivaloyloxymethylmorpholin-2-on-4-oxyl(214) A) 3,3,5-trimethyl-5-pivaloyloxymethylmorpholin-2-one

A solution of 2.63 g (0.021 mol) of pivaloyl chloride is added dropwiseto a solution of 3.5 g (0.02 mol) of3,3,5-trimethyl-5-hydroxymethylmorpholin-2-one (prepared in accordancewith J. T. Lai.: Synthesis 122 (1984)) and 0.1 g of4-dimethylaminopyridine in 20 ml of dichloromethane at 15° C. Afterstirring for 16 hours, another 0.75 ml of pivaloyl chloride is added andthe reaction mixture is stirred for 24 hours.

The reaction mixture is washed with 1 M NaHCO₃ and water and is thendried over MgSO₄ and concentrated by evaporation in a rotary evaporator.The residue is chromatographed over silica gel with hexane/ethylacetate. The pure fractions are concentrated by evaporation, giving 2.55g (50%) of the title compound, m.p. 78-81° C.

¹H-NMR (CDCl₃), δ(ppm): 4.38-4.19 m (2H), 3.99-3.89 m (2H), 1.45 s(CH₃), 1.42 s (CH₃), 1.22 s (t-Bu), 1.19 s (CH₃).

B) 3,3,5-trimethyl-5-pivaloyloxymethylmorpholin-2-on-4-oxyl

A solution of 21.5 g (0.087 mol) of m-chloroperbenzoic acid (70%) in 50ml of ethyl acetate is added dropwise, with stirring, to a solution of14.9 g (0.058 mol) of 3,3,5-trimethyl-5-pivaloyloxymethylmorpholin-2-onein 80 ml of ethyl acetate at 10° C. The reaction mixture is stirred foranother 2.5 hours at room temperature, washed with 3×120 ml of 1 MNaHCO₃ and water and is then dried over MgSO₄ and concentrated byevaporation in a rotary evaporator. The residue is recrystallised fromacetonitrile.

This gives 10.5 g (66%) of compound (214), m.p. ˜97° C.

Analysis calculated for C₁₃H₂₂NO₅: C 57.34%, H 8.14%, N 5.14%; found C57.20%, H 8.06%, N 4.96%.

Example B124-(dimethylcyanomethyloxy)-3,3,5-trimethyl-5-pivaloyloxymethylmorpholin-2-one(215)

3.35 g (0.012 mol) of3,3,5-trimethyl-5-pivaloyloxymethylmorpholin-2-on-4-oxyl and 1.5 g(0.009 mol) of azobisisobutyronitrile are refluxed for 3.5 hours undernitrogen in 15 ml of benzene. The benzene is then removed bydistillation in a rotary evaporator and the residue is recrystallisedfrom methanol.

This gives 2.67 g (65%) of compound (215), m.p. ˜86° C.

Analysis calculated for C₁₇H₂₈N₂O₅: C 59.98%, H 8.29%, N 8.23%; found C59.87%, H 8.12%, N 8.46%.

Example B13 3,3-diethyl-5-methyl-5-hydroxymethylmorpholin-2-one (216)

In analogy to Example B4 (compound 207), 3.55 g (9%) of compound (216)are obtained in the form of a colourless oil from 26.3 g (0.25 mol) of2-amino-2-methyl-1,3-propanediol, 30 ml (0.375 mol) of chloroform, 265ml (2.5 mol) of diethylketone and 50 g (1.25 mol) of sodium hydroxide.

¹H-NMR (CDCl₃), d(ppm): 4.42 d (1H), 4.07 d (1H), 3.40-3.30 m (2H),2.0-1.5 m 2×(CH₃), 1.18 s (CH₃), 0.95 m 2×(CH₃).

Example B14 3,3-diethyl-5-methyl-5-pivaloyloxymethylmorpholin-2-one(217)

2.4 ml (0.017 mol) of triethylamine and then 2.15 g 2 (0.018 mol) ofpivaloyl chloride are added dropwise to a solution of 3.45 g (0.017 mol)of 3,3-diethyl-5-methyl-5-hydroxymethylmorpholin-2-one and 0.1 g of4-dimethylaminopyridine in 20 ml dichloromethane at 15° C. Afterstirring for 20 hours, the precipitated triethylaminehydrochloride isremoved by filtration and the filtrate is washed with water, dried overMgSO₄ and concentrated by evaporation in a rotary evaporator. Theresidue is recrystallised from hexane. This gives 3.9 g (77%) ofcompound (217), m.p. 51-53° C.

Analysis calculated for C₁₅H₂₇NO₄: C 63.13%, H 9.54%, N 4.91%; found C63.08%, H 9.56%, N 5.09%.

Example B153,3-diethyl-5-methyl-5-pivaloyloxymethylmorpholin-2-on-4-oxyl (218)

A solution of 6.2 g (0.025 mol) of m-chloroperbenzoic acid (70%) in 15ml of ethyl acetate is added dropwise, with stirring, to a solution of4.8 g (0.017 mol) of3,3-diethyl-5-methyl-5-pivaloyloxymethylmorpholin-2-one in 25 ml ofethyl acetate at 10° C. The reaction mixture is stirred for another 24hours at room temperature and is then washed with 1 M NaHCO₃ and water,dried over MgSO₄ and then concentrated by evaporation in a rotaryevaporator. The residue is recrystallised from acetonitrile.

This gives 2.6 g (52%) of compound (218), m.p. 69-72° C.

Analysis calculated for C₁₅H₂₆NO₅: C 59.98%, H 8.72%, N 4.66%; found C59.91%, H 8.53%, N 4.46%.

Example B164-(α-methylbenzyloxy)-3,3-diethyl-5-methyl-5-pivaloyloxymethylmorpholin-2-one(219)

In analogy to Example B10 (compound 213), 3.14 g (93%) of compound (219)are obtained in the form of a colourless oil from 2.5 g (0.008 mol) of3,3-diethyl-5-methyl-5-pivaloyloxymethylmorpholin-2-on-4-oxyl, 6.45 ml(0.033 mol) of di-tert-butylperoxide and 200 ml of ethylbenzene.

¹H-NMR (CDCl₃), δ(ppm): 7.46-7.20 m (5arH), 4.80-4.65 m (1H), 4.2-3.9 m2×(CH₂), 2.3-1.6 m 2×(CH₂), 1.55 d (CH₃), 1.30 s (t-Bu), 0.90 m 2×(CH₃).

Example B17 3,3,5-triethyl-5-hydroxymethylmorpholin-2-one (220)

In analogy to Example B4 (compound 207), 0.5 g (0.9%) of compound (220)is obtained in the form of a colourless oil from 29.8 g (0.25 mol) of2-amino-2-ethyl-1,3-propanediol, 30 ml (0.375 mol) of chloroform, 265 ml(2.5 mol) of diethylketone and 50 g (1.25 mol) of sodium hydroxide.

¹H-NMR (CDCl₃), δ(ppm): 4.37 d (1H), 4.18 d (1H), 3.45-3.35 m (2H),1.9-1.4 m 3×(CH₂), 0.95 m 3×(CH₃).

Example B18 3,3,5-triethyl-5-pivaloyloxymethylmorpholin-2-one (221)

In analogy to Example B14 (compound (217), 8.45 g (75%) of compound(221), m.p. 37-41° C. (hexane), are obtained from 8.1 g (0.037 mol) of3,3,5-triethyl-5-hydroxymethylmorpholin-2-one, 0.2 g of4-dimethylaminopyridine, 5.3 ml (0.038 mol) of triethylamine and 5.15 ml(0.042 mol) of pivaloyl chloride.

Analysis calculated for C₁₆H₂₉NO₄: C 64.19%, H 9.76%, N 4.68%; found C64.18%, H 9.78%, N 4.82%.

Example B19 3,3,5-triethyl-5-pivaloyloxymethylmorpholin-2-on-4-oxyl(222)

In analogy to Example B15 (compound (218), 8.0 g (98%) of compound (222)are obtained in the form of a red oil from 7.8 g (0.026 mol) of3,3,5-triethyl-5-pivaloyloxymethylmorpholin-2-one and 9.6 g (0.039 mol)of m-chloroperbenzoic acid (70%).

Analysis calculated for C₁₆H₂₈NO₅: C 61.12%, H 8.98%, N-4.46%; found C60.95%, H 9.07%, N 4.35%.

Example B204-(α-methylbenzyloxy)-3,3,5-triethyl-5-pivaloyloxymethylmorpholin-2-one(223)

In analogy to Example B10 (compound 213), 7.65 g (91%) of compound (223)are obtained in the form of a colourless oil from 6.3 g (0.020 mol) of3,3,5-triethyl-5-pivaloyloxymethylmorpholin-2-on-4-oxyl, 15.5 ml (0.080mol) of di-tert-butylperoxide and 200 ml of ethylbenzene.

Analysis calculated for C₂₄H₃₇NO₅: C 68.71%, H 8.89%, N 3.34%; found C68.61%, H 8.84%, N 3.21%.

Example B21 1-isopropyl-3-ethyl-3,5,5-trimethylpiperazin-2-one (229)

40 g (1 mol) of finely ground NaOH are added, with stirring, to asolution of 24.6 g (0.189 mol) ofN-1-isopropyl-2-methylpropane-1,2-diamine (prepared in accordance withM. Senkus.: J. Am. Chem. Soc. 68, 10 (1946)) and 25 ml (0.3 mol) ofchloroform in 250 ml (2.77 mol) of methyl ethyl ketone at 10° C. Thereaction mixture is stirred for 16 hours at room temperature and is thenfiltered. The filtrate, concentrated by evaporation in a rotaryevaporator, is chromatographed over silica gel with hexane/ethyl acetate(3:2). The pure fractions are concentrated by evaporation, giving 13.7 g(33%) of compound (229) in the form of a colourless oil.

¹H-NMR (CDCl₃), δ(ppm): 4.96 m (1H), 3.0 m (CH₂), 1.9-1.4 m (CH₂), 1.35s (CH₃), 1.18 s 2×(CH₃), 1.07 d 2×(CH₃), 0.88 t (CH₃).

Example B22 1-isopropyl-3-ethyl-3,5,5-trimethylpiperazin-2-on-4-oxyl(230)

0.4 g of sodium tungstate, 2 g of sodium carbonate and then, at 10° C.,27.5 ml of hydrogen peroxide (35%, in water) are added to a solution of13.7 g (0.064 mol) of 1-isopropyl-3-ethyl-3,5,5-trimethylpiperazin-2-onein 50 ml of methanol. The reaction mixture is stirred for 40 hours atroom temperature and is then diluted with 100 ml of saturated NaClsolution and extracted with 5×50 ml of methyl-tert-butyl ether. Theextracts are dried over MgSO₄, concentrated by evaporation andchromatographed over silica gel with hexane/ethyl acetate (3:1). Thepure fractions are concentrated by evaporation, giving 9.4 g (64%) ofcompound (230) in the form of a red oil.

Analysis calculated for C₁₂H₂₃N₂O₂: C 63.40%, H 10.20%, N 12.32%; foundC 63.34%, H 10.36%, N 11.81%.

Example B234-(dimethylcyanomethyloxy)-1-isopropyl-3-ethyl-3,5,5-trimethylpiperazin-2-one(231)

4.55 g (0.02 mol) of1-isopropyl-3-ethyl-3,5,5-tetramethylpiperazine-2-on-4-oxyl and 4.93 g(0.03 mol) of azobisisobutyronitrile are refluxed for 2 hours undernitrogen in 20 ml of benzene. The benzene is then removed bydistillation in a rotary evaporator and the residue is chromatographedover silica gel with hexane/ethyl acetate (9:1). 2.25 g (38%) ofcompound (231) are obtained in the form of a colourless solid, m.p.106-108° C. Analysis calculated for C₁₆H₂₉N₃O₂: C 65.05%, H 9.89%, N14.22%; found C 65.10%, H 9.83%, N 14.27%.

Example B244-(α-methylbenzyloxy)-1-isopropyl-3-ethyl-3,5,5-trimethylpiperazin-2-one(232)

In analogy to Example B3, compound (206), 3.41 g (0.015 mol) of1-isopropyl-3-ethyl-3,5,5-trimethylpiperazin-2-on-4-oxyl are reactedwith 11 ml (0.06 mol) of t-butylperoxide and ethylbenzene as solvent,resulting in 4.55 g (91%) of the desired compound in the form of acolourless oil.

Elemental analysis calculated for C₂₀H₃₂N₂O₂: C 72.25%; H 9.70%; N8.43%. Found: C 71.80%; H 9.86%; N 8.24%.

Example B25 1-isopropyl-3,3-diethyl-5,5-dimethylpiperazin-2-one (233)

In analogy to Example B21, compound (229), 16.4 g (36%) of compound(233) are obtained in the form of a colourless oil from 26.1 g (0.2 mol)of N-1-isopropyl-2-methylpropane-1,2-diamine, 25 ml (0.3 mol) ofchloroform, 265 ml (2.5 mol) of diethylketone and 40 g (1 mol) of NaOH.

¹H-NMR (CDCl₃), δ(ppm): 4.98 m (1H), 3.0 m (CH₂), 1.8-1.4 m 2×(CH₂),1.16 s 2×(CH₃), 1.70 d 2×(CH₃), 0.88 t 2×(CH₃).

Example B26 1-isopropyl-3,3-diethyl-5,5-dimethylpiperazin-2-on-4-oxyl(234)

In analogy to Example B22, compound (230), 11.5 g (70%) of compound(234) are obtained in the form of a red oil from 15.4 g (0.07 mol) of1-isopropyl-3,3-diethyl-5,5-dimethylpiperazin-2-one, 0.4 g of sodiumtungstate, 2 g of sodium carbonate and 25 ml of hydrogen peroxide (35%,in water).

Analysis calculated for C₁₃H₂₅N₂O₂: C 64.69%, H 10.44%, N 11.61%; foundC 64.67%, H 10.44%, N 11.47%.

Example B274-(dimethylcyanomethyloxy)-1-isopropyl-3,3-diethyl-5,5-dimethylpiperazin-2-one(235)

In analogy to Example B23, compound (231), 1.64 g (53%) of compound(235) are obtained in the form of a colourless solid, m.p. 84-89° C.,from 2.41 g,(0.01 mol) of1-isopropyl-3,3-diethyl-5,5-dimethyl-piperazin-2-on-4-oxyl and 2.46 g(0.015 mol) of azobis-isobutyronitrile.

Analysis calculated for C₁₇H₃₁N₃O₂: C 65.98%, H 10.10%, N 13.58%; foundC 65.73%, H 10.04%, N 13.61%.

Example B281-isopropyl-4-(α-methylbenzyloxy)-3,3-diethyl-5,5-dimethylpiperazin-2-one(236)

In analogy to Example B10 (compound 213), 6.2 g (89%) of compound (236)are obtained in the form of a colourless oil from 4.8 g (0.020 mol) of1-isopropyl-3,3-diethyl-5,5-dimethylpiperazin-2-on-4-oxyl, 15.5 ml(0.080 mol) of di-tert-butylperoxide and 250 ml of ethylbenzene.

Analysis calculated for C₂₁H₃₄N₂O₂: C 72.79%, H 9.89%, N 8.08%; found C72.61%, H 9.89%, N 8.15%.

Example B29 1-t-butyl-3,3-diethyl-5,5-dimethylpiperazin-2-one (237)

In analogy to Example B21, compound (229), 44.2 g (66%) of compound(237) are obtained in the form of a colourless oil from 39.7 g (0.275mol) of 1,1-dimethyl-2-t-butylaminopropylamine (prepared in accordancewith G. Smith et al.: J. Chem. Soc. 886 (1962)), 33.5 ml (0.412 mol) ofchloroform, 360 ml (3.4 mol) of diethylketone and 55 g (1.375 mol) ofNaOH.

¹H-NMR (CDCl₃), δ(ppm): 3.16 s (CH₂), 1.7-1.5 m 2×(CH₂), 1.42 s (t-Bu),1.15 s 2×(CH₃), 0.89 t 2×(CH₃).

Example B30 1-t-butyl-3,3-diethyl-5,5-dimethylpiperazin-2-on-4-oxyl(238)

In analogy to Example B22, compound (230), 41 g (99%) of compound (238)are obtained in the form of a red oil from 38.9 g (0.162 mol) of1-t-butyl-3,3-diethyl-5,5-dimethylpiperazin-2-one, 1 g of sodiumtungstate, 5 g of sodium carbonate and 56 ml of hydrogen peroxide (35%,in water).

Analysis calculated for C₁₄H₂₇N₂O₂: C 65.84%, H 10.66%, N 10.97%; foundC 65.59%, H 10.87%, N 10.75%.

Example B311-t-butyl-4-(α-methylbenzyloxy)-3,3-diethyl-5,5-dimethylpiperazin-2-one(239)

In analogy to Example B10 (compound 213), 6.6 g (91%) of compound (239)are obtained in the form of a colourless oil from 5.11 g (0.020 mol) of1-t-butyl-3,3-diethyl-5,5-dimethylpiperazin-2-on-4-oxyl, 15.5 ml (0.080mol) of di-tert-butylperoxide and 300 ml of ethylbenzene.

Analysis calculated for C₂₂H₃₆N₂O₂: C 73.29%, H 10.06%, N 7.77%; found C73.41%, H 10.19%, N 7.75%.

Example B324-(dimethylcyanomethyloxy)-1-t-butyl-3,3-diethyl-5,5-dimethylpipe-razin-2-one(240)

In analogy to Example B23, compound (231), 8.7 g (67%) of compound (240)are obtained in the form of a colourless solid, m.p. 68-71° C., from10.2 g (0.04 mol) of1-t-butyl-3,3-diethyl-5,5-dimethyl-piperazin-2-on-4-oxyl and 4.9 g (0.03mol) of azobisisobutyronitrile. Analysis calculated for C₁₈H₃₃N₃O₂: C66.84%, H 10.28%, N 12.99%; found C 66.72%, H 10.08%, N 13.03%.

Example B33 3,3-diethyl-5,5,6,6-tetramethylpiperazin-2-one (241)

In analogy to Example B21, compound (229), 1.85 g (9%) of compound (241)are obtained in the form of an amorphous solid from 18.9 g (0.1 mol) of1,1,2,2-tetramethyl-1,2-ethanediamine dihydrochloride (prepared inaccordance with G. Smith et al.: J. Chem. Soc. 886 (1962)), 12.5 ml(0.15 mol) of chloroform, 235 ml (1.25 mol) of diethylketone and 20 g(0.5 mol) of NaOH.

¹H-NMR (CDCl₃), δ(ppm): 5.56 s (NH), 1.69 q 2×(CH₂),1.21 s 2×(CH₃), 1.15s2×(CH₃), 0.95 t 2×(CH₃).

Example B34 3,3-diethyl-5,5,6,6-tetramethylpiperazin-2-on-4-oxyl (242)

In analogy to Example B22, compound (230), 0.35 g (19%) of compound(242) are obtained in the form of a red solid, m.p. ˜135° C., from 1.7 g(0.008 mol) of 3,3-diethyl-5,5,6,6-tetramethylpiperazin-2-one, 0.25 g ofsodium tungstate, 0.8 g of sodium carbonate and 4.5 ml of hydrogenperoxide (35%, in water).

Example B354-(dimethylcyanomethyloxy)-3,3-diethyl-5,5,6,6-tetramethylpiperazin-2-one(243)

In analogy to Example B23, compound (231), 0.29 g (65%) of compound(243) are obtained in the form of a colourless solid, m.p. 140-145° C.,from 0.35 g (0.0015 mol) of3,3-diethyl-5,5,6,6-tetramethylpiperazin-2-on-4-oxyl and 0.25 g (0.0015mol) of azobisisobutyronitrile.

¹H-NMR (CDCl₃), δ(ppm): 5.88 s (NH), 2.3-1.8 m 2×(CH₂),1.73 s (CH₃),1.72 s (CH₃), 1.43 s (CH₃), 1.30 s (CH₃), 1.18 s (CH₃), 1.17 s (CH₃),1.05 m 2×(CH₃).

Example B36 1-benzyl-3,3-diethyl-5,5-dimethylpiperazin-2-one (244)

In analogy to Example B21, compound (229), 46.2 g (61%) of compound(244) are obtained in the form of a colourless oil from 49 g (0.275 mol)of N-1-benzyl-2-methylpropane-1,2-diamine (prepared in accordance withM. Senkus.: J. Am. Chem. Soc. 68, 10 (1946)), 25 ml (0.3 mol) ofchloroform, 360 ml (3.4 mol) of diethylketone and 55 g (1.375 mol) ofNaOH.

¹H-NMR (CDCl₃), δ(ppm): 7.28 m (C₆H₅), 4.60 s (CH₂), 3.03 s (CH₂),1.8-1.6 m 2×(CH₂), 1.07 s 2×(CH₃), 0.86 t 2×(CH₃).

Example B37 1-benzyl-3,3-diethyl-5,5-dimethylpiperazin-2-on-4-oxyl (245)

In analogy to Example B22, compound (230), 41.9 g (96%) of compound(245) are obtained in the form of a red oil from 41 g (0.15 mol) of1-benzyl-3,3-diethyl-5,5-dimethyl-piperazin-2-one, 1 g of sodiumtungstate, 5 g of sodium carbonate and 52 ml of hydrogen peroxide (35%,in water).

Analysis calculated for C₁₇H₂₅N₂O₂: C 70.56%, H 8.71%, N 9.68%; found C70.06%, H 8.34%, N 9.44%.

Example B38 1-(2-hydroxyethyl)-3,3-diethyl-5,5-dimethylpiperazin-2-one(246)

In analogy to Example B21, compound (229), 32.6 g (48%) of compound(246) are obtained in the form of a colourless oil from 39.7 g (0.3 mol)of N-(2-hydroxyethyl)-2-methyl-propane-1,2-diamine, 37 ml (0.45 mol) ofchloroform, 380 ml (3.6 mol) of diethylketone and, 60 g (1.5 mol) ofNaOH.

¹H-NMR (CDCl₃), δ(ppm): 3.78 t (CH₂), 3.55 t (CH₂), 1.8-1.6 m 2×(CH₂),1.20 s 2×(CH₃), 0.88 t 2×(CH₃).

Example B39 1-t-Butyl-3-ethyl-3,5,5-trimethyl-piperazin-2-on (247)

In analogy to Example B21, 1,1-dimethyl-2-t-butylaminoethylamin,methylethylketon, chloroform and NaOH are reacted to give the raw titlecompound (99%) as an yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.17d (CH₂), 1.8-1.6 m (CH₂), 1.42 s (t-Bu),1.34 s, 1.20 s, 1.18 s 3×(CH3), 0.89 t (CH₃).

Example B40 1-t-Butyl-3-ethyl-3,5,5-trimethyl-piperazin-2-on-4-oxyl(248)

45.3 g (0.2 Mol) of raw compound (247) are dissolved in 450 ml ofethylacetate and 51.1 ml (0.3 Mol) of peracetic acid (39% in aceticacid) are added to the stirred solution under cooling within 20 minutes.The solution is stirred for another 2.5 hours, then diluted with 100 mlof hexane and washed with NaHCO₃ solution till neutral. The titlecompound (248) is obtained after evaporation of hexane, chromatographyof the residue on Silica gel with hexane-EtOAc (5:1) and crystallizationfrom pentane. Yield 23.7 g (49%) of red crystals, m.p. 50-53° C.

Elemental analysis, for C₁₃H₂₅N₂O₂ calculated: C 64.69%, H 10.44%, N11.61%; found: C 64.58%, H 10.51%, N 11.61%.

Example B411-t-Butyl-4-(α-methylbenzyloxy)-3-ethyl-3,5,5-trimethyl-piperazin-2-on(249)

In analogy to Example B10, the compound (249) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.36-7.25 m (5 ArH), 4.76-4.65 m (1H), 3.17-2.82m (CH₂), 1.89-0.53 m (26H).

Example B42 1-t-Butyl-3,5-diethyl-3,5-dimethyl-piperazin-2-on (250)

A) 1-Ethyl-1-methyl-2-t-butylaminoethylamin

This amine has been prepared from 2-nitrobutane following the method ofG. Smith et al. (J. Chem. Soc. 886 (1962)).

B)

In analogy to Example B23, 1-ethyl-1-methyl-2-t-butylaminoethylamin,methylethylketon, chloroform and NaOH are reacted to give the raw titlecompound (100%) as an yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.25-3.08 m (CH₂), 1.7-0.84 m (25H).

Example B43 1-t-Butyl-3,5-diethyl-3,5-dimethyl-piperazin-2-on-4-oxyl(251)

In analogy to Example B40, the compound (250) is transformed into thetitle compound as a red oil.

Elemental analysis, for C₁₄H₂₇N₂O₂ calculated: C 65.84%, H 10.66%, N10.97%; found: C 65.22%, H 10.63%, N 10.97%.

Example B441-t-Butyl-4-(α-methylbenzyloxy)-3,5-diethyl-3,5-dimethyl-piperazin-2-on(252)

In analogy to Example B10, the compound (251) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.36-7.23 m (5 ArH), 4.75-4.66 m (1H), 3.20-2.84m (CH₂), 1.93-0.59 m (28H).

Example B45 1-t-Butyl-5,5-diethyl-3,3-dimethyl-piperazin-2-on (253)

A) 1,1-Diethyl-2-t-butylaminoethylamin

This amine has been prepared from 3-nitropentane following the method ofG. Smith et al. (J. Chem. Soc. 886 (1962)).

B)

In analogy to Example B21, 1,1-diethyl-2-t-butylaminoethylamin, aceton,chloroform and NaOH are reacted to give the title compound (77%) as anyellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.21 s (CH₂), 1.51-1.37 m, 2×(CH₂), 1.43 s(t-Bu), 1.36 s, 2×(CH₃), 0.85 t, 2×(CH₃).

Example B46 1-t-Butyl-5,5-diethyl-3,3-dimethyl-piperazin-2-on-4-oxyl(254)

In analogy to Example B22, the compound (253) is transformed into thetitle compound (89%) as a red crystals, m.p. 53-55° C.

Elemental analysis, for C₁₄H₂₇N₂O₂ calculated: C 65.84%, H 10.66%, N10.97%; found: C 65.98%, H 10.70%, N 11.09%.

Example B471-t-Butyl-4-(dimethylcyanomethyloxy)-5,5-diethyl-3,3-dimethylpiperazin-2-on(255)

In analogy to Example B23, the compound (254) is transformed into thetitle compound (89%) as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 3.27-3.03 m (CH₂), 1.84-1.76 m, (CH₂), 1.66 s,1.64 s, 2×(CH₃), 1.50 s, 1.49 s, 2×(CH₃), 1.46-1.41 m, (CH₂), 1.39 s(t-Bu), 0.97-0.91 m (CH₃).

Example B48 1-t-Butyl-3,5,5-triethyl-3-methyl-piperazin-2-on (256)

In analogy to Example B21, 1,1-diethyl-2-t-butylaminoethylamin,methylethylketon, chloroform and NaOH are reacted to give the titlecompound (64%) as an yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.25-3.16 m (CH₂), 2.05-1.38 m, 3×(CH₂), 1.43(CH₃), 0.93-0.83 m, 3×(CH₃).

Example B49 1-t-Butyl-3,5,5-triethyl-3-methyl-piperazin-2-on-4-oxyl(257)

In analogy to Example B22, the compound (256) is transformed into thetitle compound (88%) as a red crystals, m.p. 57-60° C.

Elemental analysis, for C₁₅H₂₉N₂O₂ calculated: C 65.84%, H 10.66%, N10.97%; found: C 66.87%, H 10.85%, N 10.40%.

Example B501-t-Butyl-4-(dimethylcyanomethyloxy)-3,5,5-triethyl-3-methyl-piperazin-2-on(258)

In analogy to Example B23, the compound (257) is transformed into thetitle compound (83%) as colorless crystals, m.p. 78-80° C.

¹H-NMR (CDCl₃), δ(ppm): 3.21-3.04 m (CH₂), 2.04-1.80 m, 2×(CH₂), 1.66 s,1.64 s, 1.45 s, 3×(CH₃), 1.41 s (t-Bu), 1.0-0.92 m (CH₃).

Example B51 1-t-Butyl-4-benzyloxy-3,5,5-triethyl-3-methyl-piperazin-2-on(259)

In analogy to Example B10 and using toluene instead of ethylbenzene, thecompound (257) is transformed into the title compound as a colorlessoil.

¹H-NMR (CDCl₃), δ(ppm): 7.39-7.28 m (5 ArH), 4.85-4.76 m (CH₂),3.13-3.08 m (CH₂), 1.92-0.86 m (27H).

Example B521-t-Butyl-4-(α-methylbenzyloxy)-3,5,5-triethyl-3-methyl-piperazin-2-on(260)

In analogy to Example B10, the compound (257) is transformed into thetitle compound as a colorless solid, m.p. 76-79° C.

Elemental analysis, for C₂₈H₃₈N₂O₂ calculated: C 73.75%, H 10.23%, N7.48%; found: C 73.51%, H 9.68%, N 7.12%.

Example B53 1-t-Butyl-3,3,5-triethyl-5-methyl-piperazin-2-on (261)

In analogy to Example B21, 1-ethyl-1-methyl-2-t-butylaminoethylamin,diethylketon, chloroform and NaOH are reacted to give the raw titlecompound (71%) as an yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.18-3.06 m (CH₂), 1.60-0.82 m (27H).

Example B54 1-t-Butyl-3,3,5-triethyl-5-methyl-piperazin-2-on-4-oxyl(262)

In analogy to Example B40, the compound (261) is transformed into thetitle compound as a red oil.

Example B551-t-Butyl-4-(α-methylbenzyloxy)-3,3,5-triethyl-5-methyl-piperazin-2-on(263)

In analogy to Example B10, the compound (262) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.37-7.28 m (5 ArH), 4.75-4.69 m (1H), 3.22-2.90m (CH₂), 2.14-0.63 m (30H).

Example B56 1-t-Butyl-3,3,5,5-tetraethyl-piperazin-2-on (264)

In analogy to Example B21, 1,1-diethyl-2-t-butylaminoethylamin,diethylketon, chloroform and NaOH are reacted to give the title compound(52%) as a yellow oil.

Elemental analysis, for C₁₆H₃₂N₂O calculated: C 71.58%, H 12.02%, N10.44%; found: C 71.38%, H 12.05%, N 10.13%.

Example B57 1-t-Butyl-3,3,5,5-tetraethyl-piperazin-2-on-4-oxyl (265)

In analogy to Example B40, the compound (264) is transformed into thetitle compound as red crystals, m.p. 34-37° C.

Elemental analysis, for C₁₆H₃₁N₂O₂ calculated: C 67.80%, H 11.02%, N9.88%; found: C 67.78%, H 11.06%, N 9.88%.

Example B58 1-t-Butyl-4-benzyloxy-3,3,5,5-tetraethyl-piperazin-2-on(266)

In analogy to Example B10 and using toluene instead of ethylbenzene, thecompound (265) is transformed into the title compound as colorlesscrystals, m.p. 83-85° C.

Elemental analysis, for C₂₃H₃₈N₂O₂ calculated: C 73.75%, H 10.23%, N7.48%; found: C 74.33%, H 10.26%, N 7.41%.

Example B591-t-Butyl-4-(α-methylbenzyloxy)-3,3,5,5-tetraethyl-piperazin-2-on (267)

In analogy to Example B10, the compound (265) is transformed into thetitle compound as colorless crystals, m.p. 85-90° C.

Elemental analysis, for C₂₄H₄₀N₂O₂ calculated: C 74.18%, H 10.38%, N7.21%; found: C 74.40%, H 10.44%, N 7.08%.

Example B601-t-Butyl-4-(dimethylcyanomethyloxy)-3,3,5,5-tetraethyl-piperazin-2-on(268)

In analogy to Example B23, the compound (265) is transformed into thetitle compound as colorless crystals, m.p. 45-52° C.

Elemental analysis, for C₂₀H₃₇N₃O₂ calculated: C 68.33%, H 10.61%, N11.95%; found: C 68.33%, H 10.67%, N 11.84%.

Example B61 1-t-Butyl-3,3-cyclohexyliden-5,5-diethyl-piperazin-2-on(269)

In analogy to Example B21, 1,1-diethyl-2-t-butylaminoethylamin,cyclohexanon, chloroform and NaOH are reacted to give the title compoundas a yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.16 s (CH₂), 2.26-0.82 m (20H), 1.41 s (t-Bu).

Example B621-t-Butyl-3,3-cyclohexyliden-5,5-diethyl-piperazin-2-on-4-oxyl (270)

In analogy to Example B22, the compound (269) is transformed into thetitle compound as a red oil.

Example B631-t-Butyl-3,3-cyclohexyliden-4-(α-methylbenzyloxy)-5,5-diethyl-piperazin-2-on-4-oxyl(271)

In analogy to Example B10, the compound (270) is transformed into thetitle compound as colorless crystals, m.p. 93-96° C.

Elemental analysis, for C₂₅H₄₀N₂O₂calculated: C 74.96%, H 10.06%, N6.99%; found: C 74.79%, H 9.69%, N 6.66%.

Example B64 1-t-Butyl-3,3-dipropyl-5,5-dimethyl-piperazin-2-on (272)

In analogy to Example B21, 1,1-dimethyl-2-t-butylaminoethylamin,dipropylketon, chloroform and NaOH are reacted to give the titlecompound as a yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.22 s (CH₂), 1.7-0.8 m (20H), 1.41 s (t-Bu).

Example B65 1-t-Butyl-3,3-dipropyl-5,5-dimethyl-piperazin-2-on-4-oxyl(273)

In analogy to Example B10, the compound (272) is transformed into thetitle compound as colorless crystals, m.p. 67-70° C.

Elemental analysis, for C₁₆H₃₁N₂O₂calculated: C 67.80%, H 11.02%, N9.88%; found: C 67.69%, H 10.77%, N 9.87%.

Example B661-t-Butyl-4-(dimethylcyanomethyloxy)-3,3-dipropyl-5,5-dimethyl-piperazin-2-on(274)

In analogy to Example B23, the compound (273) is transformed into thetitle compound as colorless crystals, m.p. 85-87° C.

Elemental analysis, for C₂₀H₃₇N₃O₂ calculated: C 68.34%, H 10.61%, N11.95%; found: C 68.32%, H 10.50%, N 12.05%.

Example B67 1-t-Butyl-3,3-dipropyl-5,5-diethyl-piperazin-2-on (275)

In analogy to Example B21, 1,1-diethyl-2-t-butylaminoethylamin,dipropylketon, chloroform and NaOH are reacted to give the titlecompound as a yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.14 s (CH₂), 1.7-0.8 m (24H), 1.41 s (t-Bu).

Example B68 1-t-Butyl-3,3-dipropyl-5,5-diethyl-piperazin-2-on-4-oxyl(276)

In analogy to Example B22, the compound (275) is transformed into thetitle compound as red crystals, m.p. 62-64° C.

Elemental analysis, for C₁₈H₃₅N₂O₂ calculated: C 69.41%, H 11.33%, N8.99%; found: C 68.37%, H 11.50%, N 9.04%.

Example B691-t-Butyl-3,3-dipropyl-4-(α-methylbenzyloxy)-5,5-diethyl-piperazin-2-on(277)

In analogy to Example B10, the compound (276) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.37-7.22 m (5 ArH), 4.75-4.64 m (1H), 3.21-2.96m (CH₂), 2.1-0.62 m (36H).

Example B70 1-t-Butyl-3,3-dibutyl-5,5-dimethyl-piperazin-2-on (278)

In analogy to Example B21, 1,1-dimethyl-2-t-butylaminoethylamin,dibutylketon, chloroform and NaOH are reacted to give the title compoundas a yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.16 s (CH₂),1.7-0.8 m (24H), 1.42 s (t-Bu).

Example B71 1-t-Butyl-3,3-dibutyl-5,5-dimethyl-piperazin-2-on-4-oxyl(279)

In analogy to Example B22, the compound (278) is transformed into thetitle compound as red crystals, m.p. 36-48° C.

Elemental analysis, for C₁₈H₃₅N₂O₂ calculated: C 69.41%, H 11.33%, N8.99%; found: C 69.35%, H 11.09%, N 9.04%.

Example B721-t-Butyl-3,3-dibutyl-4-(dimethylcyanomethyloxy)-5,5-dimethyl-piperazin-2-on(280)

In analogy to Example B23, the compound (279) is transformed into thetitle compound as colorless crystals, m.p. 68-74° C.

¹H-NMR (CDCl₃), δ(ppm): 3.18-3.04 m (CH₂), 2.1-0.8 m (30H), 1.40 s(t-Bu).

Example B73 1-t-Octyl-3,3-diethyl-5,5-dimethyl-piperazin-2-on (281)

In analogy to Example B21, 1,1-dimethyl-2-t-octylaminoethylamin,diethylketon, chloroform and NaOH are reacted to give the title compoundas a yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.17 s (CH₂), 1.9-0.8 m (31H).

Example B74 1-t-Octyl-3,3-diethyl-5,5-dimethyl-piperazin-2-on-4-oxyl(282)

In analogy to Example B22, the compound (281) is transformed into thetitle compound as red crystals, m.p. 54-56° C.

Elemental analysis, for C₁₈H₃₅N₂O₂ calculated: C 69.41%, H 11.33%, N8.99%; found: C 69.43%, H 11.39%, N 9.03%.

Example B751-t-Octyl-3,3-diethyl-4-(dimethylcyanomethyloxy)-5,5-dimethyl-piperazin-2-on(283)

In analogy to Example B23, the compound (282) is transformed into thetitle compound as colorless crystals, m.p. 49-53° C.

Elemental analysis, for C₂₂H₄₁N₃O₂ calculated C 69.61%, H 10.89%, N11.07%; found: C 69.60%, H 10.73%, N 11.22%.

Example B761-t-Octyl-3,3-diethyl-4-(α-methylbenzyloxy)-5,5-dimethyl-piperazin-2-on(284)

In analogy to Example B10, the compound (283) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.49-7.38 m (5 ArH), 4.86-4.81 m (1H), 3.27-3.03m (CH₂), 2.3-0.7 m (36H).

Example B771-(2-Hydroxyethyl)-3,3-diethyl-5,5-dimethyl-piperazin-2-on-4-oxyl (285)

In analogy to Example B22, the compound (246) is transformed into thetitle compound as a red oil.

Elemental analysis, for C₁₂H₂₃N₂O₃ calculated: C 59.23%, H 9.53%, N11.51%; found: C 59.17%, H 9.52%, N 11.34%.

Example B781-(2-Hydroxyethyl)-3,3-diethyl-4-(dimethylcyanomethyloxy)-5,5-dimethylpiperazin-2-on(286)

In analogy to Example B23, the compound (285) is transformed into thetitle compound as colorless crystals, m.p. 80-82° C.

Elemental analysis, for C₁₆H₂₉N₃O₃ calculated: C 61.71%, H 9.39%, N13.49%; found: C 61.69%, H 9.58%, N 13.39%.

Example B791-(1,1-Dimethyl-2-hydroxyethyl)-3,3-diethyl-5,5-dimethyl-piperazin-2-on(287)

In analogy to Example B21, 1,1-dimethyl-2-hydroxyethylamin,diethylketon, chloroform and NaOH are reacted to give the title compoundas a yellow oil.

¹H-NMR (CDCl₃), δ(ppm): 3.73 s (CH₂), 3.15 s (CH₂), 1.7-0.8 m (22H).

Example B801-(1,1-Dimethyl-2-hydroxyethyl)-3,3-diethyl-5,5-dimethyl-piperazin-2-on-4-oxyl(288)

In analogy to Example B22, the compound (287) is transformed into thetitle compound as a red oil.

Elemental analysis, for C₁₄H₂₇N₂O₃ calculated: C 61.96%, H 10.03%, N10.32%; found: C 61.96%, H 9.92%, N 10.27%.

Example B811-(1,1-Dimethyl-2-hydroxyethyl)-3,3-diethyl-4-(dimethylcyanomethyloxy)-5,5-dimethyl-piperazin-2-on(289)

In analogy to Example B23, the compound (288) is transformed into thetitle compound as colorless crystals, m.p. 58-66° C.

Elemental analysis, for C₁₈H₃₃N₃O₃calculated: C 63.69%, H 9.80%, N12.38%; found: C 63.79%, H 9.75%, N 12.37%.

Example B82 1-t-Butyl-3,3-diethyl-4-allyloxy-5,5-dimethyl-piperazin-2-on(290)

A) 1-t-Butyl-3,3-diethyl-4-hydroxy-5,5-dimethyl-piperazin-2-on

50.1 g (0.196 Mol) of the nitroxide (238) are hydrogenated in amethanolic solution at r.t. over Pt at 1 bar H₂ untill the hydrogenuptake stops. The catalyst is filtered off and the solvent is evaporatedto give the crude title hydroxylamine.

B)

To a solution of 10.25 g (0.04 Mol) of the above hydroxylamine in 40 mldimethylformamide are added 2.1 g (0.048 Mol) of NaH (60% in Oil). After1 hour stirring, 5.81 g (0.048 Mol) of allylbromide are added and themixture is stirred for another 3 h. The title compound (9.7 g, 82%) isobtained after dilution with water, extraction with methyl-t-butyletherand chromatography on silicagel (hexane-EtOAc 2:1) as a colorless oil.

Elemental analysis, for C₁₇H₃₂N₂O₂calculated: C 68.88%, H 10.88%, N9.45%; found: C 68.99%, H 10.85%, N 9.50%.

Example B83 1-t-Butyl-3,3-diethyl-4-benzyloxy-5,5-dimethyl-piperazin-2-on (291)

In analogy to Example B82 and using benzylbromide instead ofallylbromide, the title compound is prepared as a colorless oil.

Elemental analysis, for C₂₁H₃₄N₂O₂calculated: C 72.79%, H 9.89%, N8.08%; found: C 72.63%, H 9.73%, N 8.05%.

Example B841-t-Butyl-3,3-diethyl-4-(α-cyanocyclohexyloxy)-5,5-dimethyl-piperazin-2-on(292)

2.8 g (0.011 Mol) of1-t-butyl-3,3-diethyl-5,5-dimethyl-piperazin-2-on-4-oxyl (compound 238)and 2.0 g (0.0082 Mol) 1,1′-azobis-(cyclohexancarbonitril) are stirredat 100° C. in 12 ml of chlorobenzene under nitrogen for 11 h.Afterwards, the solvent is evaporated under vacuum and the semisolidresidue is taken up in hexane. Filtration affords 2.2 g (55%) of thetitle compound as colorless crystals, m.p. 94-98° C.

Elemental analysis, for C₂₁H₃₇N₃O₂ calculated: C 69.38%, H 10.26%, N11.56%; found: C 69.85%, H 9.89%, N 11.82%.

Example B851-t-Butyl-3,3-diethyl-4-α-methyl-4-acetylbenzyl)-5,5-dimethyl-piperazin-2-on(293)

In analogy to Example B10 and using 4-ethylacetophenon instead ofethylbenzene, the nitroxide (238) is transformed into the title compoundas colorless crystals, m.p. 91-94° C.

Elemental analysis, for C₂₄H₃₈N₂O₃: calculated C 71.60%, H 9,51%, N6.96%; found C %71.03, H 9.49%, N 6.90%.

Example B861-t-Butyl-3,3-diethyl-4-(α-methyl-4-acetoxybenzyl)-5,5-dimethylpiperazin-2-on(294)

In analogy to Example B10 and using 4-acetoxyethylbenzene instead ofethylbenzene, the nitroxide (238) is transformed into the title compoundas colorless crystals, m.p. 92-96° C.

Elemental analysis, for C₂₄H₃₈N₂O₄ calculated C 68.86%, H 9.15, N 6.69,found C 68.68%, 9.10%, N 6.46%.

Example B87 1-Phenyl-3,3-diethyl-5,5-dimethyl-piperazin-2-on (295)

In analogy to Example B21, 1,1-dimethyl-2-phenylaminoethylamin (preparedaccording H. G. Johnson, J. Am. Chem. Soc. 68,14 (1946)), diethylketon,chloroform and NaOH are reacted to give the title compound as colorlesssolid, m.p. 54-56° C.

¹H-NMR (CDCl₃), δ(ppm): 7.18-7.0 m (5 ArH), 3.31 s (CH₂),1.73-1.43 m(4H), 1.06 s 2×(CH₃), 0.75 t, 2×(CH3).

Example B88 1-Phenyl-3,3-diethyl-5,5-dimethyl-piperazin-2-on-4-oxyl(296)

In analogy to Example B40, the compound (295) is transformed into thetitle compound as red crystals, m.p. 71-76° C.

Elemental analysis, for C₁₆H₂₃N₂O₂ calculated: C 69.79%, H 8.42%, N10.17%; found: C 70.04%, H 8.74%, N 10.19%.

Example B891-Phenyl-3,3-diethyl-4-(α-methylbenzyloxy)-5,5-dimethyl-piperazin-2-on(297)

In analogy to Example B10, the compound (296) is transformed into thetitle compound as colorless crystals, m.p. 78-81° C.

Elemental analysis, for C₂₄H₃₂N₂O₂ calculated: C 75.75%, H 8.48%, N7.36%; found: C 75.83%, H 8.52%, N 7.50%.

Example B90 1-Methyl-3,3-diethyl-5,5-dimethyl-piperazin-2-on (298)

In analogy to Example B21, 1,1-Dimethyl-2-methylaminoethylamin (preparedaccording M. Senkus, J. Am. Chem. Soc. 68,10 (1946)), diethylketon,chloroform and NaOH are reacted to give the title compound as acolorless oil.

¹H-NMR (CDCl₃), δ(ppm): 3.14 s (CH₂), 2.80 s (CH₃),1.8-0.7 m (10H), 1.18s, 2×(CH₃),

Example B91 1-Methyl-3,3-diethyl-5,5-dimethyl-piperazin-2-on-4-oxyl(299)

In analogy to Example B40, the compound (298) is transformed into thetitle compound as red crystals, m.p. 72-76° C.

Example B921-Methyl-3,3-diethyl-4-(α-methylbenzyloxy)-5,5-dimethyl-piperazin-2-on(1200)

In analogy to Example B10, the compound (299) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.28-7.19 m (5 ArH), 4.70-4.61m (1H), 3.27-2.6 m(CH₂), 2.83 s (CH₃), 2.2-0.5 m (19H).

Example B93 1-t-Butyl-3-isobutyl-3,5,5-trimethyl-piperazin-2-on (1201)

In analogy to Example B21, 1,1-dimethyl-2-t-butylaminoethylamin,methylisobutylketon, chloroform and NaOH are reacted to give the titlecompound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 3.17 s (CH₂),1.75-0.85 m (18H), 1.35 s, (t-Bu).

Example B94 1-t-Butyl-3-isobutyl-3,5,5-trimethyl-piperazin-2-on-4-oxyl(1202)

In analogy to Example B40, the compound (1201) is transformed into thetitle compound as red crystals, m.p. 32-37° C.

Example B951-t-Butyl-3-isobutyl-4-(α-methylbenzyloxy)-3,5,5-trimethyl-piperazin-2-on(1203)

In analogy to Example B10, the compound (1202) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.38-7.26 m (5 ArH), 4.81-4.74m (1H), 3.21-2.87m (CH₂), 2.1-0.65 m (21H), 1.40 s (t-Bu).

7-ring Compounds

Example C11-(dimethylcyanomethyloxy)-2,2,7,7-tetramethyl-[1,4]diazepan-5-one (301)

In analogy to Example B23, compound (231), 0.75 g (12%) of compound(301) are obtained in the form of a colourless solid, m.p. 130-134° C.,from 4.6 g (0.025 mol) of 2,2,7,7-tetramethyl-[1,4]diazepan-5-on-1-oxyl(prepared in accordance to E. G. Rozantsev et al.: Izv. Akad. Nauk SSSR,Ser. Khim. 2114 (1980)) and 3.08 g (0.018 mol) ofazobisisobutyronitrile. Analysis calculated for C₁₃H₂₃N₃O₂: C 61.63%, H9.15%, N 16.59%; found C 61.41%, H 8.91%, N 16.73%.

Example C2 1-(α-methylbenzyloxy)-2,2,7,7-tetramethyl-[1,4]diazepan-5-one(302)

In analogy to Example B3, compound (206), 5.0 g (0.027 mol) of2,2,7,7-tetramethyl-[1,4]diazepan-5-on-1-oxyl (prepared in accordancewith E. G. Rozantsev et al.: Izv. Akad. Nauk SSSR, Ser. Khim. 2114(1980)) are reacted with 20.9 ml (0.113 mol) of t-butylperoxide andethylbenzene as solvent, resulting in 3.7 g (48%) of the desiredcompound in the form of a colourless solid, m.p. 125-127° C.

Analysis calculated for C₁₇H₂₆N₂O₂: C 70.31%, H 9.02%, N 9.65%; found C69.99%, H 8.90%, N 9.56%.

Example C3 2,3,7-Trimethyl-2,7-diethyl-[1,4]diazepan-5-one-1-oxyl (303)

This nitroxide has been made according to DE 2621924.

Example C41-Benzyloxy-4-benzyl-2,3,7-trimethyl-2,7-diethyl-[1,4]diazepan-5-one(304)

A) 1-Hydroxy-2.3.7-trimethyl-2.7-diethyl-[1.4]diazepan-5-one

The solution of 4.55 g (0.02 Mol) of the nitroxide (303) in 20 ml ofethylacetate is during 3 h vigorously stirred with the solution of 7.9 g(0.04 Mol) of sodium ascorbate in 25 ml of water. The colorless organiclayer is then separated, dried over MgSO₄ and evaporated in vacuum togive the title hydroxylamine as an amorphous, off white solid.

B)

8.0 g (0.035 Mol) of the preceding hydroxylamine are reacted asdescribed in Example B83 with 10.4 ml (0.087 Mol) of benzylbromide and3.8 g (0.0875 Mol) of NaH (55%) to afford 10.8 g (75%) of the titlecompound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.37-7.24 m (10 ArH), 5.03 s(CH₂), 4.86-4.84 m(CH₂), 3.34-2.90 m (CH₂), 2.5-0.77 m (20H).

Example C51-Allyloxy-4-allyl-2,3,7-trimethyl-2,7-diethyl-[1,4]diazepan-5-one (305)

In analogy to example C4 but using allylbromide instead ofbenzylbromide, the title compound is prepared as a colorless oil.

Elemental analysis, for C₁₈H₃₂N₂O₂ calculated: C 70.09%, H 10.46%, N9.08%; found: C 70.21%, H 10.72%, N 9.09%.

Example C6 2,3,4,7-Tetramethyl-2,7-diethyl-[1,4]diazepan-5-one-1-oxyl(306)

A solution of 2.25 g (0.009Mol)2,3,7-trimethyl-2,7-diethyl-[1,4]diazepan-5-one-1-oxyl (303), 0.45 gtetrabutylammoniumhydrogensulfate and 9 ml methyliodide in 40 ml CH₂Cl₂is stirred vigorously during 5 h with 64 g of 50% aqueous sodiumhydroxide. The organic layer is then separated, washed with water andchromatographed on silica gel with hexane-EtOAc (9:1) to give 1.95 g(81%) of the title compound as a red oil.

Example C71-(α-Methylbenzyloxy)-2,3,4,7-tetramethyl-2,7-diethyl-[1,4]diazepan-5-one(307)

In analogy to Example B10, the compound (306) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.34-7.08 m (5 ArH), 4.61-4.52 m (1H), 3.61 bs(CH₃), 2.3-0.45 m (25H).

Example C82,3,7-Trimethyl-2,7-diethyl-4-t-butyloxycarbonyl-[1,4]diazepan-5-one-1-oxyl(308)

To a solution of 13.1 g (0.06 Mol) of di-t-butyldicarbonate and 0.15 g4-dimethylaminopyridine in 30 ml THF is slowly added the solution of11.3 g (0.05 Mol) of the nitroxide (303) in 20 ml THF. The mixture isthen stirred 16 h at r.t. and then evaporated. The residue is dissolvedin CH₂Cl₂, washed with water, dried over MgSO₄ and evaporated again togive the title compound as a red oil.

Example C91-(α-Methylbenzyloxy)-2,3,7-trimethyl-2,7-diethyl-4-t-butyloxycarbo-nyl-[1,4]diazepan-5-one-(309)

In analogy to Example B10, the compound (308) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.35-6.9 m (5 ArH), 4.58-4.51 m (1H), 2.3-0.45 m(25H), 1.29 s (t-Bu).

Example C101-(α-Methylbenzyloxy)-2,3,7-trimethyl-2,7-diethyl-[1,4]diazepan-5-one-(310)

To a solution of 2 g (0.0046 Mol) of the BOC-derivative (309) in 8 mlCH₂Cl₂ are added 2 ml of CF₃COOH and the mixture is stirred 19 h at r.t.The title compound (1.1 g) is obtained after dilution with water,washing with NaHCO₃ solution, drying over MgSO₄ and evaporation as acolorless resin.

¹H-NMR (CDCl₃), δ(ppm): 7.35-6.9 m (5 ArH), 4.58-4.51 m (1H), 2.3-0.45 m(25H).

Example C114-Benzyl-2,3,7-trimethyl-2,7-diethyl-[1,4]diazepan-5-one-1-oxyl (311)

In analogy to Example C6 and using benzylchloride instead ofmethyliodide the compound (303) is transformed into the title compoundas a red oil.

Example C12 1-Butyl-3,3,5,5,7-pentamethyl-[1,4]diazepan-2-one-4-oxyl(312)

In analogy to Example B40, the1-butyl-3,3,5,5,7-pentamethyl-[1,4]diazepan-2-one (prepared as describedby Pyong-nae Son, J. T. Lai.: J. Org. Chem. 46, 323 (1981)) istransformed into the title compound as a red oil.

Example C131-Butyl-4-(α-methylbenzyloxy)-3,3,5,5,7-pentamethyl-[1,4]diazepan-2-one(313)

In analogy to Example B10, the compound (312) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.33-7.10 m (5 ArH), 4.66-4.55 m (1H), 4.20—4.10m (1H), 3.13-3.01 m (CH₂), 1.6-0.5 m (27H).

Example C14 1-Butyl-3-ethyl-3,5,5,7-tetramethyl-[1,4]diazepan-2-one(314)

The title compound was prepared as described by Pyong-nae Son, J. T.Lai.: J. Org. Chem. 46, 323 (1981) for1-butyl-3,3,5,5,7-pentamethyl-[1,4]diazepan-2-one, but usingmethylethylketon instead of acetone.

Colorless oil, ¹H-NMR (CDCl₃), δ(ppm): 4.15-3.79 m (1H), 3.21-2.89 m(CH₂), 1.7-0.6 m (26H).

Example C151-Butyl-3-ethyl-3,5,5,7-tetramethyl-[1,4]diazepan-2-one-4-oxyl (315)

In analogy to Example B40, the compound (314) is transformed into thetitle compound as a red oil.

Example C161-Butyl-3-ethyl-4-(α-methylbenzyloxy)-3,5,5,7-tetramethyl-[1,4]diaze-pan-2-one(316)

In analogy to Example B10, the compound (315) is transformed into thetitle compound as a colorless oil.

¹H-NMR (CDCl₃), δ(ppm): 7.33-7.10 m (5 ArH), 4.74-4.66 m (1H), 4.40-4.34m (1H), 3.24-3.18 m (CH₂), 2.3-0.5 m (29H).

The compounds prepared are summarized in Tables 1 to 3.

TABLE 1 5-ring compounds No. Structure 101

102

103

104

105

106

TABLE 2 6-ring compounds No. Structure 204

205

206

207

208

209

210

211

212

213

214

215

216

217

218

219

220

221

222

223

229

230

231

232

233

234

235

236

237

238

239

240

241

242

243

244

245

246

247

248

249

250

251

252

253

254

255

256

257

258

259

260

261

262

263

264

265

266

267

268

269

270

271

272

273

274

275

276

277

278

279

280

281

282

283

284

285

286

287

288

289

290

291

292

293

294

295

296

297

298

299

1200

1201

1202

1203

TABLE 3 7-ring compounds No. Structure 301

302

303 NE 2854

304 NE 3032 CG 38-1117

305 NE 3012 CG 38-1091

306 NE 3134

307 NE 3135 CG 39-0186

308 NE 3198

309 NE 3202 CG 39-0400

310 NE 3203 CG 39-0401

311

312

313

314

315

316

POLYMERIZATION EXAMPLES

Experimental runs of the polymerizations using the regulators listed inTables 1-3:

General remarks:

Shortly before use, all solvents and monomers are distilled over aVigreux column under argon or under vacuum.

Before polymerization, all reaction mixtures are freed from oxygen byrinsing with argon using the thaw/freeze technique and are then keptunder argon gas.

Before the start of the polymerization reaction, the reagents are in theform of a clear homogeneous solution.

The monomer reaction is determined by weighing the residue afterunreacted monomer has been evaporated at 80° C. and 0.02 torr over somehours until a constant weight is reached and drawing off the regulatorused.

The polymers are characterised by GPC (gel permeation chromatography).

MALDI-MS: the measurements are carried out on a linear TOF (time offlight)

MALDI-MS LDI-1700, of Linear Scientific Inc., Reno, USA. The matrix usedis 2,5-dihydroxybenzoic acid and the laser wavelength is 337 nm.

GPC: A two-flask series pump RHEOS 4000, of FLUX INSTRUMENTS(represented by Ercatech A G, Berne, Switzerland), is used. The pumpcapacity is 1 ml/min. The chromatography is carried out on twoseries-switched PIgel 5 μm mixed-C type columns, of POLYMER INSTRUMENTS,Shropshire, UK, at 40° C. in THF. These columns are calibrated withpolystyrene at Mn from 200 to 2000000. The fractions are measured usingan RI detector ERC-7515A, of ERCATECH AG, at 30° C.

1-P) Controlled Polymerization of n-butylacrylate with Compound (105) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 329 mg (1.2 mmol) ofcompound (106) and 10 g (78 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 2 g (20%)of the monomer are reacted and a clear, colourless, viscous liquid isobtained.

GPC: Mn=1500, Mw=2000, polydispersity molecular weight distribution=1.3

2-P) Controlled Polymerization of n-butylacrylate with Compound (106) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 373 mg (1.2 mmol) ofcompound (107) and 10 g (78 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 5.8 g(58%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=5000, Mw=8900, polydispersity molecular weight distribution =1.8

3-P) Controlled Polymerization of n-butylacrylate with Compound (209) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 471 mg (1.7 mmol) ofcompound (209) and 15 g (117 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 3 g (20%)of the monomer are reacted and a clear, yellow, viscous liquid isobtained.

GPC: Mn=1600, Mw=2000, polydispersity molecular weight distribution=1.25

4-P) Controlled Polymerization of n-butylacrylate with Compound (210) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 536 mg (1.7 mmol) ofcompound (210) and 15 g (117 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 11.55 g(77%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=6300, Mw=8700, polydispersity molecular weight distribution =1.4

5-P) Controlled Polymerization of n-butylacrylate with Compound (213) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 780 mg (2.3 mmol) ofcompound (213) and 20 g (156 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 19.6 g(98%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=6100, Mw=11700, polydispersity molecular weight distribution=1.9

6-P) Controlled Polymerization of n-butylacrylate with Compound (213) at130° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 780 mg (2.3 mmol) ofcompound (213) and 20 g (156 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 130° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 130° C.The mixture is stirred for 5 hours at 130° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 18 g (90%)of the monomer are reacted and a clear, colourless, viscous liquid isobtained.

GPC: Mn=7500, Mw=11000, polydispersity molecular weightdistribution=1.45

7-P) Controlled Polymerization of n-butylacrylate with Compound (213) at120° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 780 mg (2.3 mmol) ofcompound (213) and 20 g (156 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 120° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 120° C.The mixture is stirred for 5 hours at 120° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 10.4 g(52%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=5000, Mw=6750, polydispersity molecular weight distribution=1.35

8-P) Controlled Polymerization of n-butylacrylate with Compound (219) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 949 mg (2.3 mmol) ofcompound (219) and 20 g (156 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 18.6 g(93%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=6500, Mw=14500, polydispersity molecular weight distribution=2.2

9-P) Controlled Polymerization of n-butylacrylate with Compound (219) at130° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 949 mg (2.3 mmol) ofcompound (219) and 20 g (156 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 130° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 130° C.The mixture is stirred for 5 hours at 130° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 18.6 g(93%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=7100, Mw=16200, polydispersity molecular weight distribution=2.3

10-P) Controlled Polymerization of n-butylacrylate with Compound (219)at 120° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 4740 mg (1.2 mmol) ofcompound (219) and 10 g (78 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 120° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 120° C.The mixture is stirred for 5 hours at 120° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 8.7 g(87%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=8100, Mw=17700, polydispersity molecular weight distribution=2.2

11-P) Controlled Polymerization of n-butylacrylate with Compound (223)at 145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirred, is charged with 982 mg (2.3 mmol) ofcompound (223) and 20 g (156 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 18.6 g(93%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=6600, Mw=10300, polydispersity molecular weightdistribution=1.56

12-P) Controlled Polymerization of n-butylacrylate with Compound (231)at 145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 502 mg (1.7 mmol) ofcompound (231) and 15 g (117 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 3.3 g(22%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=2000, Mw=2500, polydispersity molecular weight distribution=1.2

13-P) Controlled Polymerization of n-butylacrylate with Compound (232)at 145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 565 mg (1.7 mmol) ofcompound (232) and 15 g (117 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 11.1 g(74%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=6000, Mw=13200, polydispersity molecular weight distribution=2.2

14-P) Controled Polymerization of n-butylacrylate with Compound (235) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 543 mg (1.7 mmol) ofcompound (235) and 15 g (117 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 7.95 g(53%) of the monomer are reacted and a clear, colourless, viscous liquidis obtained.

GPC: Mn=4500, Mw=5200, polydispersity molecular weight distribution=1.15

15-P) Controlled polymerization of n-butylacrylate with compound (236)at 145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 405 mg (1.2 mmol) ofcompound (236) and 10 g (78 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 8.1 g(81%) of the monomer are reacted and a clear, yellow, viscous liquid isobtained.

GPC: Mn=6900, Mw=8800, polydispersity molecular weight distribution=1.3

16P) Controlled Polymerization of n-butylacrylate with Compound (239) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 422 mg (1.2 mmol) ofcompound (239) and 10 g (78 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 8.1 g(81%) of the monomer are reacted and a clear, yellow, viscous liquid isobtained.

GPC: Mn=6700, Mw=8700, polydispersity molecular weight distribution=1.3

17P) Controlled Polymerization of n-butylacrylate with Compound (240) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 378 mg (1.2 mmol) ofcompound (240) and 10 g (78 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 7.4 g(74%) of the monomer are reacted and a clear, yellow, viscous liquid isobtained.

GPC: Mn=5800, Mw=7000, polydispersity molecular weight distribution=1.2

18P) Controlled Polymerization of n-butylacrylate with Compound (243) at145° C.

A 50 ml round-bottom three-neck flask, equipped with thermometer,condenser and magnetic stirrer, is charged with 276 mg (0.9 mmol) ofcompound (243) and 8 g (62 mmol) of n-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The polymerizationstarts spontaneously and the temperature in the vessel rises to 145° C.The mixture is stirred for 5 hours at 145° C. and is then cooled to 60°C. and the remaining monomer is evaporated under high vacuum. 5.9 g(74%) of the monomer are reacted and a clear, yellow, viscous liquid isobtained.

GPC: Mn=6700, Mw=8100, polydispersity molecular weight distribution=1.2

19P) Controlled Polymerization of Butadiene with the Compound (239)

An autoclave is charged with 6, 85 g (0,019 mol) of the compound (239)and 54,0 g (1 mol) of butadiene. The reaction mixture is then heated for5 hours to 145° C. After cooling to room temperature the remainingbutatiene is evaporated under vacuum. 4.65 g of a clear slight yellowviscous fluid is obtained.

GPC: Mn=1400 Mw=1620 Polydispersity(PD)=1.16

20P) Block Copolymer Butadiene/n-butylacrylate

In a 50 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 1,6 g (2 mol %) of the butadiene macroinitiator fromthe preceding example and 10 g of n-butylacrylate are mixed. The clearsolution obtained is purged with argon and stirred for 5 hours at 145°C. The reaction mixture is then cooled to 60° C. The remaining monomeris removed be evaporation under vacuum. 5.7 g (40%) of the initialmonomer have reacted. A clear slight yellow viscous fluid is obtained.

GPC: Mn=4150 Mw=5670 Polydispersity(PD)=1.36

21P) Controlled Polymerization of n-butylacrylate with the Compound(249)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.405 g (1.17 mmol)(1.5Mol %) of compound (249) and 10 g (78 mmol) of n-butylacrylate anddegassed. The colourless solution is then heated to 145° C. under argon.The mixture is stirred for 5 hours at 145° C. and then cooled to 60° C.and the remaining monomer is evaporated under high vacuum. 7.2 g (72%)of the monomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=5000 Mw=13000 Polydispersity(PD)=2.6

22P) Controlled Polymerization of n-butylacrylate with the Compound(252)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.422 g (1.17 mmol) ofcompound (252) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7.0 g (70%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn 6500 Mw=8800 Polydispersity(PD)=1.35

23P) Controlled Polymerization of n-butylacrylate with the Compound(255)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.378 g (1.17 mmol) ofcompound (255) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 5.1 g (51%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=4650 Mw=5600 Polydispersity(PD)=1.2

24P) Controlled Polymerization of n-butylacrylate with the Compound(258) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.395 g (1.17 mmol) ofcompound (258) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8 g (80%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6400 Mw=8950 Polydispersity(PD)=1.4

25P) Controlled Polymerization of n-butylacrylate with the Compound(258) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.395 (1.17 mmol) ofcompound (258) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 5 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 3.2 g (32%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=2600 Mw=8950 Polydispersity(PD)=1.2

26P) Controlled Polymerization of n-butylacrylate with the Compound(259) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.422 g (1.17 mmol) ofcompound (259) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 9 g (90%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6900 Mw=19300 Polydispersity(PD)=2.8

27P) Controlled Polymerization of n-butylacrylate with the Compound(259) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.422 g (1.17 mmol) ofcompound (259) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 5 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 5.1 g (51%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6100 Mw=12200 Polydispersity(PD)=2.0

28P) Controlled Polymerization of n-butylacrylate with the Compound(260) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 g (1.17 mmol) ofcompound (260) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 6.7 g (67%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6000 Mw=7200 Polydispersity(PD)=1.2

29P) Controlled Polymerization of n-butylacrylate with the Compound(260) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 (1.17 mmol) ofcompound (260) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 5 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 4.7 g (47%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=3300 Mw=3950 Polydispersity(PD)=1.2

30P) Controlled Polymerization of n-butylacrylate with the Compound(263) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 g (1.17 mmol) ofcompound (263) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 9 g (90%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7700 Mw=10800 Polydispersity(PD)=1.4

31P) Controlled Polymerization of n-butylacrylate with the Compound(263) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 g (1.17 mmol) ofcompound (263) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 5 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 2.6 g (26%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=2500 Mw=3000 Polydispersity(PD)=1.2

32P) Controlled Polymerization of n-butylacrylate with the Compound(263) at 100° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 g (1.17 mmol) ofcompound (263) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 100° C. under argon. The mixtureis stirred for 48 hours at 100° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 5 g (50%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=4000 Mw=5100 Polydispersity(PD)=1.3

33P) Controlled Polymerization of n-butylacrylate with the Compound(266) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 g (1.17 mmol) ofcompound (266) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 1 hour at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8.5 g (85%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7500 Mw=14250 Polydispersity(PD)=1.9

34P) Controlled Polymerization of n-butylacrylate with the Compound(266) at 100° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 g (1.17 mmol) ofcompound (266) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 100° C. under argon. The mixtureis stirred for 5 hours at 100° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7 g (70%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6000 Mw=9000 Polydispersity(PD)=1.5

35P) Controlled Polymerization of n-butylacrylate with the Compound(267) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.455 g (1.17 mmol) ofcompound (267) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 2 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8.7 g (87%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7100 Mw=8500 Polydispersity(PD)=1.2

36P) Controlled Polymerization of n-butylacrylate with the Compound(267) at 100° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.455 g (1.17 mmol) ofcompound (267) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 100° C. under argon. The mixtureis stirred for 5 hours at 100° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8.7 g (87%) of themonomer are reacted and a colourless viscous liquid is obtained.

After 2 hours GPC: Mn=1600 Mw=2100 Polydispersity(PD)=1.3 (22% yield)

After 5 hours: GPC: Mn=2400 Mw=3100 Polydispersity(PD)=1.3 (31% yield)

37P) Controlled Polymerization of n-butylacrylate with the Compound(268) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.411 g (1.17 mmol) ofcompound (268) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 1 hour at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7.7 g (77%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6500 Mw=7800 Polydispersity(PD)=1.2

38P) Controlled Polymerization of n-butylacrylate with the Compound(268) at 100° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.411 g (1.17 mmol) ofcompound (268) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 100C under argon. The mixture isstirred for 5 hours at 100° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 1.7 g (17%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=1400 Mw=1500 Polydispersity(PD)=1.1

39P) Controlled Polymerization of n-butylacrylate with the Compound(271)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.469 g (1.17 mmol) ofcompound (271) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7.5 g (75%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7900 Mw=10360 Polydispersity(PD)=1.3

40P) Controlled Polymerization of n-butylacrylate with the Compound(274)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.411 g (1.17 mmol) ofcompound (274) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8.5 g (85%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6400 Mw=8300 Polydispersity(PD)=1.3

41P) Controlled Polymerization of n-butylacrylate with the Compound(277) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.487 (1.17 mmol) ofcompound (277) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 5 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 9 g (90%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7300 Mw=9500 Polydispersity(PD)=1.3

42P) Controlled Polymerization of n-butylacrylate with the Compound(277) at 110° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.487 g (1.17 mmol) ofcompound (277) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 110° C. under argon. The mixtureis stirred for 5 hours at 110° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7 g (70%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6100 Mw=7900 Polydispersity(PD)=1.3

43P) Controlled Polymerization of n-butylacrylate with the Compound(277) at 100° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.487 g (1.17 mmol) ofcompound (277) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 100° C. under argon. The mixtureis stirred for 48 hours at 100° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7 g (70%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: after 5 hours: 37% yield, Mn=3300 Mw=4300 Polydispersity(PD)=1.3

after 48 hours: 70% yield, Mn=6500 Mw=9500 Polydispersity(PD)=1.2

44P) Controlled Polymerization of n-butylacrylate with the Compound(280)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.430 g (1.17 mmol) ofcompound (280) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7.5 g (75%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6000 Mw=7200 Polydispersity(PD)=1.2

45P) Controlled Polymerization of n-butylacrylate with the Compound(283)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.409 g (1.17 mmol) ofcompound (283) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7 g (70%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6000 Mw=7100 Polydispersity(PD)=1.2

46P) Controlled Polymerization of n-butylacrylate with the Compound(284)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.487 g (1.17 mmol) ofcompound (284) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8 g (80%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7500 Mw=112500 Polydispersity(PD)=1.5

47P) Controlled Polymerization of n-butylacrylate with the Compound(286)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.364 g (1.17 mmol) ofcompound (286) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 12 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. A clear slight yellowviscous liquid is obtained.

GPC:  5 hours: 54% yield Mn = 4900 Mw = 5700 Polydispersity(PD) = 1.1 12hours: 84% yield Mn = 6800 Mw = 9200 Polydispersity(PD) = 1.4

48P) Controlled Polymerization of n-butylacrylate with the Compound(289)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.314 g (1.17 mmol) ofcompound (289) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7 g (70%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6100 Mw=7300 Polydispersity(PD)=1.2

49P) Controlled Polymerization of n-butylacrylate with the Compound(290)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.347 g (1.17 mmol) ofcompound (290) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 9 g (90%) of themonomer are reacted and a clear slight yellow viscous liquid isobtained.

GPC: Mn=8800 Mw=15000 Polydispersity(PD)=1.7

50P) Controlled Polymerization of n-butylacrylate with the Compound(291)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.346 g (1.17 mmol) ofcompound (291) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 9.4 g (94%) of themonomer are reacted and a clear slight yellow viscous liquid isobtained.

GPC: Mn=7000 Mw=16000 Polydispersity(PD)=2.2

51P) Controlled Polymerization of n-butylacrylate with the Compound(292)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.425 g (1.17 mmol) ofcompound (292) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8.7 g (87%) of themonomer are reacted and a clear slight yellow viscous liquid isobtained.

GPC: Mn=7200 Mw=10100 Polydispersity(PD)=1.4

52P) Controlled Polymerization of n-butylacrylate with the Compound(293) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.471 g (1.17 mmol) ofcompound (293) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7.2 g (72%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6400 Mw=9000 Polydispersity(PD)=1.4

53P) Controlled Polymerization of n-butylacrylate with the Compound(293) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.471 g (1.17 mmol) ofcompound (293) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 5 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 2.8 g (28%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=2400 Mw=3350 Polydispersity(PD)=1.4

54P) Controlled Polymerization of n-butylacrylate with the Compound(294)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.373 g (1.17 mmol) ofcompound (294) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8 g (80%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=9900 Mw=17800 Polydispersity(PD)=1.8

55P) Controlled Polymerization of n-butylacrylate with the Compound(297)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.445 g (1.17 mmol) ofcompound (297) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 9 g (90%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6400 Mw=9000 Polydispersity(PD)=1.4

56P) Controlled Polymerization of n-butylacrylate with the Compound(1200)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.373 g (1.17 mmol) ofcompound (1200) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7.7 g (77%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7700 Mw=10800 Polydispersity(PD)=1.4

57P) Controlled Polymerization of n-butylacrylate with the Compound(1203)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 g (1.17 mmol) ofcompound (1203) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 7.8 g (78%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7500 Mw=12750 Polydispersity(PD)=1.7

58P) Controlled Polymerization of n-butylacrylate with the Compound(304)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.447 g (1.17 mmol) ofcompound (304) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8 g (80%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7000 Mw=11 900 Polydispersity(PD)=1.7

59P) Controlled Polymerization of n-butylacrylate with the Compound(305)

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.357 g (1.17 mmol) ofcompound (305) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 6.5 g (65%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=6600 Mw=9900 Polydispersity(PD)=1.5

60P) Controlled Polymerization of n-butylacrylate with the Compound(307) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.405 g (1.17 mmol) ofcompound (307) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8.6 g (86%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7100 Mw=10600 Polydispersity(PD)=1.5

61P) Controlled Polymerization of n-butylacrylate with the Compound(307) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.405 g (1.17 mmol) ofcompound (307) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 5 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 3.7 g (37%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=3400 Mw=4400 Polydispersity(PD)=1.3

62P) Controlled Polymerization of n-Butylacrylate with the Compound(309) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.506 g (1.17 mmol) ofcompound (309) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 9 g (90%) of themonomer are reacted and a yellow viscous liquid is obtained.

GPC: Mn=9100 Mw=19100 Polydispersity(PD)=2.1

63P) Controlled Polymerization of n-butylacrylate with the Compound(309) at 130° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.506 g (1.17 mmol) ofcompound (309) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8 g (80%) of themonomer are reacted and a yellow viscous liquid is obtained.

GPC: Mn=9100 Mw=19100 Polydispersity(PD)=2.1

64P) Controlled Polymerization of n-butylacrylate with the Compound(310) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.389 g (1.17 mmol) ofcompound (310) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 8 g (80%) of themonomer are reacted and a yellow viscous liquid is obtained.

GPC: Mn=10600 Mw=21200 Polydispersity(PD)=2.0

65P) Controlled Polymerization of n-butylacrylate with the Compound(310) at 130° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.389 g (1.17 mmol) ofcompound (310) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 130° C. under argon. The mixtureis stirred for 5 hours at 130° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 5.5 g (55%) of themonomer are reacted and a yellow viscous liquid is obtained.

GPC: Mn=5300 Mw=9000 Polydispersity(PD)=1.7

66P) Controlled Polymerization of n-butylacrylate with the Compound(313) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.422 g (1.17 mmol) ofcompound (313) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 9.2 g (92%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7900 Mw=12600 Polydispersity(PD)=1.6

67P) Controlled Polymerization of n-butylacrylate with the Compound(313) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.422 g (1.17 mmol) ofcompound (313) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 5 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 4 g (40%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=4300 Mw=6000 Polydispersity(PD)=1.4

68P) Controlled Polymerization of n-butylacrylate with the Compound(316) at 145° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 g (1.17 mmol) ofcompound (316) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 145° C. under argon. The mixtureis stirred for 5 hours at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 9.2 g (92%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=7700 Mw=11500 Polydispersity(PD)=1.5

69P) Controlled Polymerization of n-butylacrylate with the Compound(316) at 120° C.

A 50 ml round bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.438 g (1.17 mmol) ofcompound (316) and 10 g (78 mmol) of n-butylacrylate and degassed. Thecolourless solution is then heated to 120° C. under argon. The mixtureis stirred for 5 hours at 120° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 5.3 g (53%) of themonomer are reacted and a colourless viscous liquid is obtained.

GPC: Mn=5400 Mw=7000 Polydispersity(PD)=1.3

What is claimed is:
 1. A compound of formula (IIa) or (IIb)

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄ togetherwith the linking carbon atom form a C₃-C₁₂cycloalkyl radical; with theproviso that if Q in formula (IIa) is —CH₂— or CO, at least one of R₁,R₂, R₃ or R₄ is different from methyl; R₅, R₆ and R₇ independently arehydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl; X is selected from the groupconsisting of —CH(aryl)₂, —CH₂-aryl,

 —CH₂—CH₂-aryl,

 (C₅-C₆cycloalkyl)₂CCN, C₅-C₆cycloalkylidene-CCN, (C₁-C₁₂alkyl)₂CCN,—CH₂CH═CH₂, (C₁C₁₂)alkyl-CR₃₀—C(O)—(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₆-C₁₀)aryl,(C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₁C₁₂)alkoxy, (C₁-C₁₂)alkyl-CR₃₀—C(O)phenoxy,(C₁-C₁₂)alkyl-CR₃₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₃₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₃₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

 —O—C(O)—C₁-C₁₂alkyl, —O—C(O)—(C₆-C₁₀)aryl, (C₁-C₁₂)alkyl-CR₃₀-CN,

 wherein R₃₀ is hydrogen or C₁-C₁₂alkyl; Z₁ is O or NR₈; R₈ is hydrogen,OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl which are substituted by one or more OH,halogen or a group —O—C(O)—R₅, C₂-C₁₈alkyl which is interrupted by leastone O atom and/or NR₅ group, C₃-C₁₂cycloalkyl or C₆-C₁₀alkyl,C₇-C₉phenylalkyl, C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl, —O—C₁-C₁₈alkyl or—COOC₁-C₁₈alkyl; Q is a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ are independently hydrogen, phenyl or C₁-C₁₈alkyl, and the arylgroups are phenyl or naphthyl which are unsubstituted or substitutedwith C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkylcarbonyl,glycidyloxy, OH, —COOH or —COOC₁-C₁₂alkyl.
 2. A compound according toclaim 1 of formula (IId), (IIe), (IIf), (IIg) or (IIh)

wherein R₁ to R₁₂ have the meaning as defined in claim 1 and X isselected from the group consisting of —CH₂—phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂ and O—C(O)-phenyl.3. A compound of formula (IIIa) or (IIIb)

wherein R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₅, C₂C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄ togetherwith the linking carbon atom form a C₃-C₁₂cycloalkyl radical; R₅, R₆ andR₇ independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl; Z₁ is O orNR₈; R₈ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl which are substituted by OH,halogen or a group —O—C(O)—R₅, C₂C₁₈alkyl which is interrupted by atleast one O atom and/or NR₅ group, C₃-C₁₂cycloalkyl or C₆-C₁₀aryl,C₇C₉phenylalkyl, C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl, —O—C₁-C₁₈alkyl or—COOC₁-C₁₈alkyl; Q is a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ are independently hydrogen, phenyl or C₁-C₁₈alkyl; with theproviso that in formula (IIIa) if Q is CH₂ and Z₁ is O, at least one ofR₁, R₂, R₃ or R₄ is higher alkyl than methyl; or if Q is CH₂ or C(O) andZ₁ is NR₈ at least two of R₁, R₂, R₃ or R₄ are higher alkyl than methylor one is higher alkyl than methyl and R₁ and R₂ or R₃ and R₄ form aC₃-C₁₂cycloalkyl radical together with the linking carbon atom.
 4. Acompound according to claim 3, wherein R₁, R₂, R₃ and R₄ independentlyof each other are C₁-C₄alkyl, which is unsubstituted or substituted byOH or a group —O—C(O)—R₅; R₅ is hydrogen or C₁-C₄alkyl; R₆ and R₇independently are hydrogen, methyl or ethyl; Z₁ is O or NR₈; Q is adivalent radical CH₂, CH₂CH₂, CH₂—CH₂—CH₂, C(O), CH₂C(O) or CH₂—CH—CH₃;R₈ is hydrogen, C₁-C₄alkyl or C₁-C₄alkyl which is substituted by OH, orbenzyl.
 5. A compound of formula (IVa) or (IVb)

wherein R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₅, C₂C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl; R₅, R₆ and R₇ independently arehydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl; Z₁ is O or NR₈; R₈ is hydrogen, OH,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃C₁₈alkenyl,C₃-C₁₈alkinyl which are substituted by one or more OH, halogen or agroup —O—C(O)—R₅, C₂C₁₈alkyl which is interrupted by at least one O atomand/or NR₅ group, C₃-C₁₂cycloalkyl or C₆-C₁₀aryl, C₇C₉phenylalkyl,C₅C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl, —O—C₁-C₁₈alkyl or —COOC₁-C₁₈alkyl; Qis a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂, CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O)or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are independentlyhydrogen, phenyl or C₁-C₁₈alkyl; with the proviso that if the compoundsof formula (IVa) or (IVb) represent a 6 or 7 membered ring at least twoof R₁, R₂, R₃ and R₄ are different from methyl and the substitutionpatterns R₁, R₂, R₃, R₄ being; methyl, methyl, butyl, butyl or methyl,ethyl, methyl, ethyl are excluded.
 6. A compound according to claim 5,wherein R₁, R₂, R₃ and R₄ independently of each other are C₁-C₄alkyl,which is unsubstituted or substituted by OH or a group —O—C(O)—R₅, R₅ ishydrogen or C₁-C₄alkyl; R₆ and R₇ independently are hydrogen, methyl orethyl; Z₁ is O or NR₈; Q is a divalent radical CH₂, CH₂CH₂, CH₂—CH₂—CH₂,C(O), CH₂C(O) or CH₂—CH—CH₃; R₈ is hydrogen, C₁-C₄alkyl or C₁-C₄alkylwhich is substituted by OH, or benzyl.
 7. A compound according to claim5 wherein at least three of R₁, R₂, R₃ and R₄ are different from methyl.8. A compound according to claim 1, wherein in formula (IIa) and (IIb)R₁, R₂, R₃ and R₄ independently of each other are C₁-C₆alkyl, which isunsubstituted or substituted by OH, halogen or a group —O—C(O)—R₅,C₂-C₁₂alkyl which is interrupted by at least one O atom and/or NR₅group, C₅-C₆cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄together with the linking carbon atom form a C₅-C₆cycloalkyl radical. 9.A compound according to claim 1, wherein in formula (IIa) and (IIb) R₁,R₂, R₃ and R₄ independently of each other are C₁-C₄alkyl, which isunsubstituted or substituted by OH, or a group —O—C(O)—R₅, or R₁ and R₂and/or R₃ and R₄ together with the linking carbon atom form aC₅-C₆cycloalkyl radical; and R₅ is hydrogen or C₁-C₄alkyl.
 10. Acompound according to claim 1, wherein in formula (IIb) R₆ and R₇independently are hydrogen, methyl or ethyl.
 11. A compound according toclaim 1, wherein in formula (IIa) and (IIb) R₈ is hydrogen, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by OH; or C₇C₉phenylalkyl.
 12. Acompound according to claim 1, wherein in formula (IIa) and (IIb) R₈ ishydrogen, C₁-C₄alkyl, C₁-C₄alkyl which is substituted by OH; phenyl orbenzyl.
 13. A compound according to claim 1, wherein in formula (IIa)and (IIb) R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are independently hydrogen orC₁-C₄alkyl.
 14. A compound according to claim 1, wherein in formula(IIa) and (IIb) Q is a divalent radical CH₂, CH₂—CH₂, CH₂—CH₂—CH₂, C(O)or CH₂C(O), CH₂—CH—CH₃, CH₂—CH-phenyl, phenyl-CH—CH₂—CH-phenyl,phenyl-CH—CH₂—CH—CH₃, CH₂—CH(CH)₃—CH₂, C(CH₃)₂—CH₂—CH-phenyl orC(CH₃)₂—CH₂—CH—CH₃.
 15. A compound according to claim 1, wherein informula (IIa) and (IIb) X is selected from the group consisting of—CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl, (CH₃)₂CCN, —CH₂CH═CH₂,CH₃CH—CH═CH₂ and O—C(O)-phenyl.
 16. A compound according to claim 1,wherein in formula (IIa) and (IIb) R₁, R₂, R₃ and R₄ independently ofeach other are C₁-C₃alkyl, which is unsubstituted or substituted by OH,or a group —O—C(O)—R₅, or R₁ and R₂ and/or R₃ and R₄ together with thelinking carbon atom form a C₅-C₆cycloalkyl radical; R₅ is hydrogen orC₁-C₄alkyl; R₆ and R₇ independently are hydrogen, methyl or ethyl; Z₁ isO or NR₈; Q is a divalent radical CH₂, CH₂CH₂, CH₂—CH₂—CH₂, C(O),CH₂C(O) or CH₂—CH—CH₃; R₈ is hydrogen, C₁-C₄alkyl, C₁-C₄alkyl which issubstituted by OH, or benzyl; and X is selected from the groupconsisting of CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl, (CH₃)₂CCN,CH₂CH═CH₂, CH₃CH—CH═CH₂.
 17. A compound according to claim 1, wherein informula (IIa) and (IIb) at least two of R₁, R₂, R₃ and R₄ are ethyl,propyl or butyl and the remaining are methyl; or R₁ and R₂ or R₃ and R₄together with the linking carbon atom form a C₅-C₆cycloalkyl radical andone of the remaining substituents is ethyl, propyl or butyl.
 18. Acompound according to claim 2, wherein the compound is of formula (IId),(IIe), (Ig) or (Ih).
 19. A compound according to claim 2, wherein R₁,R₂, R₃ and R₄ independently of each other are C₁-C₃alkyl, which isunsubstituted or substituted by OH, or a group —O—C(O)—R₅, or R₁ and R₂and/or R₃ and R₄ together with the linking carbon atom form aC₅-C₆cycloalkyl radical; R₅ is hydrogen or C₁-C₄alkyl; R₆ and R₇independently are hydrogen, methyl or ethyl; R₈ is hydrogen, C₁-C₄alkyl,C₁-C₄alkyl which is substituted by OH, or benzyl; R₉, R₁₀, R₁₁ and R₁₂are independently hydrogen or C₁-C₄alkyl; and X is selected from thegroup consisting of CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl, (CH₃)₂CCN,CH₂CH═CH₂, CH₃CH—CH═CH₂.
 20. A compound according to claim 2, whereinthe compound is of formula (IIe); R₁, R₂, R₃ and R₄ independently ofeach other are C₁-C₃alkyl, which is unsubstituted or substitute by OH,or a group —O—C(O)—R₅, R₅ is hydrogen or C₁-C₄alkyl; R₈ is hydrogen,C₁-C₄alkyl, C₁-C₄alkyl which is substituted by OH, or benzyl; R₉ and R₁₀are hydrogen; and X is selected from the group consisting of CH₂-phenyl,CH₃CH-phenyl, (CH₃)₂C-phenyl, (CH₃)₂CCN, CH₂CH═CH₂, CH₃CH—CH═CH₂.
 21. Acompound according to claim 3 wherein the compound is of formula (IIId),(IIIe), (IIIf), (IIIg) or (IIIh)